ALDEHYDES & KETONES

48

LESSON

15

ALDEHYDES & KETONES

Introduction
Aldehydes are the compounds which have general formula RCHO, Ketones are compounds having general formula RR CO. The groups R and R may be aliphatic or aromatic, similar or different al yl!aryl groups.

H R

C=O

R R

C=O

An aldehyde

A etone

"oth aldehydes and etones contain the carbonyl group, C = O, and are often referred to collectively as carbonyl compounds. #t is the carbonyl group that governs mainly the chemistry of aldehydes and etones.

Structure of Carbonyl Group

Carbonyl carbon is $oined to three other atoms by bonds% since these bonds utili&e sp ' orbitals, they lie in a plane, and are (')* apart. The remaining p+orbitals of carbon overlaps a p+orbital of o,ygen to form a bond% carbon and o,ygen are thus $oined by a double bond. The part of the molecule immediately surrounding carbonyl carbon lie in a plane.

R R

C=O
(')

The electrons of a carbonyl double bond hold together atoms of -uite different electronegativity and hence the electrons are not e-ually shared% in particular the polar + cloud is pulled strongly towards the more electronegative atom, o,ygen. The carbonyl group, C = O, governs the chemistry of aldehydes and etones. #t does this in two ways . /a0 "y providing a site for nucleophilic addition, and

.1 R R
C=O

ALDEHYDES & KETONES /b0 "y increasing the acidity of hydrogen atoms attached to the alpha carbon.

49

H sp ' 8 R C C R 8 88 H O
sp 7

Physical Properties
The polar carbonyl group ma es aldehydes and etones as polar compounds and hence they have higher boiling points than non+polar compounds of comparable 2.3. "y themselves they are not capable of intermolecular hydrogen bonding since they contain hydrogen bonded only to carbon% as a result they have lower boiling points than comparable alcohols or carbo,ylic acids. For example

Compare

n+butyraldehyde methyl ethyl etone

with n+pentane

( b.p. 9:* ) ( b.p. ;)* ) ( b.p. 7:* ) ( b.p. 74* )

n+butyl alcohol propionic acid

( b.p. ((;* ) ( b.p. (<(*)

diethylether

The lower aldehydes and etones are appreciably soluble in water, because of hydrogen bonding between solute and solvent molecules% borderline solubility is reached at about 4 carbons. Aldehydes and etones are soluble in the usual organic solvents. 5ormaldehyde is a gas /b.p 6 '(*0 and is handled either as an a-ueous solution /5ormation0, or as one of its solid polymer . paraformaldehyde ( CH ' O ) n , or trio,ane,

( CH 'O ) 7 .

O CH O.CH .O.CH O ' ' ' =araformaldehyde n CH ' 8 O CH ' 8 O

Trio,ane

CH '

Acetaldehyde /b.p. ')*0 is often generated from its higher+boiling trimer by heating the trimer with acid.

H 8 7CH 7 C = O
b.p. ')*

H+

C H 7C 8 O C

H C 8 CH 7 O
CH 7

=araldehyde b.p. ('4*

ALDEHYDES & KETONES

50

CPP (. 3hich of the following etones is more acidic and why>

O 88

O 88

Preparation
A few of the many laboratory methods of preparation of aldehydes and etones are outlined below% /most of these are already familiar to us0 #ndustrial preparation is generally patterned after these laboratory methods, but with use of cheaper reagents alcohols are o,idi&ed catalytically with air, or by dehydrogenation over hot copper. Preparation of Aldehydes Oxidation of primary alcohols /"y special distillation method0 H 8 K ' Cr' O9 RCH ' OH R C = O
( alcohol Aldehyde
=.C.C. RCH 'OH R CHO CH ' Cl '

@ H+

CrO Cl

/=yridinium chloro+chromate0 /=.C.C.0

Example :
K 'Cr' O9 , H '?O < CH7CH ' CH ' OH CH 7CH ' CHO warm

Oxidation of methyl benzenes

Cl' heat h

ArCH 7

ArCHCl '

H 'O Hydrolysis

ArCH/O C CH 7 0 ' 88 O
CrO7 , acetic anhydride
A gem+diacetate ( @ot o,idi&ed )

H'O

ArCHO

ALDEHYDES & KETONES Example :

"r
Cl' , heat "r CH 7 light CaCO7 , H ' O "r CHCl '

51

CHO

p+"romotoluene

p+"romoben&aldehyde
H'O O ' @ CH ( OAc ) ' H '?O<

O ' @

CrO7 O ' @ CH 7 Ac ' O

CHO

p+nitrotoluene

p+@itroben&aldehyde

Reduction of acid chlorides

H' COCl or RCOCl =d "a?O <

CHO or RCHO

=oisoned with -uinoline+? /trace0 RosenmundBs reaction

Reimer-Tiemann Reaction-Phenolic Aldehydes /Aiscussed under phenol0 By heating a mixture of the calcium salts of formic acid and any one of its homologues.

( RCO ' ) ' Ca + ( HCO ' ) ' Ca

Stephen s !ethod

'RCHO + 'CaCO 7

(. ?nCl' + HCl R C @ RCHO '. H ' O

H ' O /Hydrolysis of intermediate0 RCH = @H to RCHO and @H 7 Preparation of Ketones Oxidation of Secondary alcohols
CrO7 or R CH R R C R K 'Cr' O9 , H '?O < 8 88 OH O

H OH

K ' Cr' O 9 H '?O <

CPP '. ?uggest the suitable reagents for the following conversions. CH 7CH 'CH 'CH 'CHO /a0 CH 7CH 'CH 'CH 'CH 'OH /b0 CH 7CH ' CH 'CHCH 7 CH 7CH 'CH ' COCH 7 8 OH CH 7CH 'CH = CHCHO /c0 CH 7CH 'CH = CHCH 'OH

ALDEHYDES & KETONES "riedel#$rafts acylation

O

52

/a0

R C

Acid chloride

Anhy. AlCl7 + ArH R C Ar + HCl or other Cewis acid 88 Cl O

Ketone

/b0

CH 7 C Cl + 88 O CH 7 CH ' C Cl + 88 O

Anhy. AlCl7 CH 7 C 88 O

+ HCl

/c0

Anhy. AlCl7 + HCl CH 7CH ' C 88 O 1n Hg% conc. HCl

CH 7CH ' CH '

/free from rearrangement0

/d0

Anhy. AlCl7 C Cl + 88 O

"en&ophenone

C 88 O

+ HCl

/e0

( CH7CO ) ' O +
Acetic anhydride

Anhy. AlCl7 CH 7 C 88 O

+ CH 7CO ' H

/f0

O 88 C O+ C 88 O CH '
Anhy. (. AlCl7 , '. H 5.C. Acylation
D

O 88 C
1n+Hg% conc. HCl ClemmsenBs Reduction ?OCl'

CO ' H

CO ' H

Anhy. AlCl7 ( #ntramolecular 5.C. Acylation )

C Cl

88 O
Anhy. AlCl7

Cl

88 O

/#ntramolecular 5.C. Acylation0

88 O

ALDEHYDES & KETONES Acylation of Al%enes R O 8 88 R C Cl + H 'C = CHR ER C CH ' CHClF R C CH = CHR 88 88 O O This is 2ar ovni ov addition initiated by R C = O , an acylium cation. &ith Organometalics /a0 Reaction of acid chlorides with organocadmium compounds R ' Cd + R C R or Ar C R RCOCl 88 88 or O O ArCOCl R must be aryl or primary al yl
+

53

Example :

( CH7CH 'CH 'CH ' ) ' Cd + 'CH7 CH ' C Cl

CH 7 8 'CH7CH ' CH 'CH ' C CH CH 7 88 O
'+2ethyl+7+heptanone

88 O

Illustration

Convert

H 7C

H 7C "r COCH 'CH 'CH 7

H7C 2g"r + CdCl'
'

Solution

H 7C

H 7C
2g "r

Cd + 'CH 7CH 'CH 'COCl H7C

CCH 'CH 'CH 7 88 O

By heating the calcium salt of any monocarboxylic acid other than formic acid
R 'CO + CaCO7 ( RCO' ) ' Ca

ALDEHYDES & KETONES Example :

CH 7COCH 7 + CaCO 7 ( CH7 C O ) ' Ca

54

88 O Acetoacetic ester synthesis of %etones

@aOGt

R H CH 7 COCH ' COOC ' H 4 CH 7CO CH CO ' CH ' CH 7 CH 7 C CHCO ' CH ' CH 7 88 8 Acetoacetic ester O R OH H CH 7 COCHCO CH 7 CO CH CO ' H CH 7COCH ' R ' ()) C 8 8 R R
+

@a +

Rin Ketones from !icarboxylic acids and their !eri"ati"es CO ' H

( CH ' ) n
CO ' H
n = < and 4

( CH ' ) n C = O + "aCO7 + H ' O

Cyclopentanone or cyclohe,anone

Al#yne hydration $discussed under Al#ynes%

Conversion of other functional groups to aldehydes /Remembering these, will help you in conversion0 R CH ' OH RCHO R CO ' H RCOCl Ar CH 7 ArCHO ArCO' H ArCOCl RR CHOH R CO ' H RCOCl ArH
AlCl7 RCOCl R Cd

=reparation of aliphatic aldehydes

=reparation of aliphatic aldehydes

R C R 88 O

=reparation of aliphatic etones

RCOCl or Ar COCl

Ar"r Ar2g"r Ar'CA ArCO' H ArCOCl

( Ar COCl )

( Ar ) ' Cd
Or R ' Cd

Ar C R 88 =reparation of O aromatic etones or Ar C Ar 88 O

ALDEHYDES & KETONES

55

CPP 7. #dentify A, " and C

O&onolysis A

O CHO + HCHO

O
O&onolysis " '

CHO CHO

C C : H4CH 'CH 'CH 'COC : H 4 + C: H 4CH 'CH 'COCH 'C :H 4

acid catalysed hydration

<.

3hich of the following carbonyl compounds when treated with dilute acid forms a stable cation>

O 88 /a0 H 7C I C I CH 7

/b0

/c0 4. /H0 will be. /a0

/d0

/b0

/c0 :.

/d0

Arrange the stability of given gemdiols in decreasing order.

/a0 ### J ## J #

/b0 # J ## J ###

/c0 ### J # J ##

/d0 ## J ### J #

ALDEHYDES & KETONES Preparation of aldehydes by oxidation methods

56

Aldehydes are easily o,idised to carbo,ylic acids by the same reagent acidic dichromate, in their synthesis. Hence, removal of aldehyde as fast as it is formed to be accomplished. ?o it is best to use =.C.C. in CH ' Cl ' a selective reagent that does not further o,idi&e the aldehydes to the acids. #n the case of toluene, o,idation of the side chain can be interrupted by trapping the aldehyde in the form a non+o,idisable derivative, the gem+diacetate, which can be isolated and then hydrolysed.
acetic ArCH7 ArCH anhydride

A+gem+diacetate /@ot o,idised0

O C CH 7 88 O O C CH 7 88 O

hydrolysis ArCHO

Preparation of Ketones by Friedel Crafts Acylation An acyl group, RCO becomes attached to the aromatic ring
O

+ R C
Cl

AlCl7 Ar C R + HCl 88 O

Illustration

Convert

@O ' CH7 C 88 O @O '

Solution
K2nO< CH 7 H+ H@O7 , H '?O < CO ' H

CO ' H O 88 C

@O '
=Cl4

@O ' COCl AlCl7

Ao not follow the route given below .

@O '
AlCl7 C Cl @o reaction 88 O A strongly deactivated ben&ene ring in nitroben&ene does not undergo 5.C. acylation or al ylation. Conversion of acyl group into al yl group can be accomplished by Clemmensen Reduction and 3olff+Kishner reduction. 5or e,ample.

ALDEHYDES & KETONES

( ) C CH 7 Conc. HCl 88 O /Clemmensen Reduction0
1n Hg

57

CH 'CH 7

Reactions of Aldehydes and Ketones

&xidation /a0
K2nO < or K 'Cr' O9 R CH = O R CO ' H

or Ar CH = O /b0 TollenLs Reagent

or ArCO' H
+

A specific o,idant for RCHO is Ag ( @H7 ) '

+

R C H + Ag ( @H 7 ) ' RCOOH 88 O TollenLs test chiefly used for the detection of aldehydes. /c0 TollenLs reagent does not attac carbon+carbon double bonds. ?trong O,idants Ketones resist mild o,idation, but with strong o,idants at high temperature they undergo cleavage of C C bonds on either sides of the carbonyl group.
b o,idation R CH ' C CH ' R ( drastic ) RCO ' H + R CH ' CO ' H + RCH ' CO ' H + R CO ' H 88 5rom cleavage of bond /a0 5rom cleavage of bond /b0 O Haloform Reaction a

/d0

CH 7 C R 88 O are readily o,idi&ed by @aO# ( @aOH + # ' ) to iodoform, CH#7 , and RCO ' @a Example :
C ' H4 C CH 7 + @aOH + # ' C ' H 4CO ' @a + + CH# 7 88 #odoform yellow% mp ((K* O Reduction

/a0

Reduction to alcohols

8 C = O

8 C OH CiAlH < or @a"H < % 8 H

H ' + =t or =d or

ALDEHYDES & KETONES

58

Aldehydes ( alcohols% Ketones ' alcohols Example :

H ' , =t CH 7 CH ' CHO CH 'CH 'CH 'OH

Red

Red

(. CiAlH < CH 7CH 'CH 'OH '. HD

Acetophenone '* alcohol

CiAlH < C CH 7 88 O H
+

OH 8 C CH7 8 H

/b0

Reduction to hydrocarbons 8 1n ( Hg ) , Conc. HCl C H 8 H > C = O 8 @H ' @H ' , base C H 8 H

Clemmensen reduction for compounds sensitive to base

3olff+Kishner reaction for compounds sensitive to acids

Illustration

?uggest a mechanism for the following conversions.

O 88 H 7C
Solution

OH 8

CH 7 O 88
H
+

8 CH 7 OH + 88

CH 7 OH 8 H 8 CH 7
+

OH 8 H+ 8 CH 7 CH 7

CH 7

CH 7

H 7C

CH 7

CH 7

Addition Reactions of Carbonyl Compounds The C of the carbonyl group is electrophilic and initially forms a bond with the nucleophile

C= O C O

ALDEHYDES & KETONES

59

sp ' C = O + @u

sp7
8 H+ C O C OH 8 8 @u @u

8 + @u H+ C OH C = O > C OH 8 @u

C = OH
/a0 Addition of cyanide

CH 7 O CH 7 88 8 8 + H 7O H ' O' ! H '?O < CH C CO ' H CH 7 C CH 7 + @aC@ CH 7 C C@ 7 boil 8 8 OH OH

Acetone cyanohydrin

Heat

CH 7 8 CH ' = C CO ' H
2ethylacrylic acid /'+2ethylpropenoic acid0

CPP 9. Two organic compounds /A0 and /"0 with molecular formula C7 H : O, react with HC@ is different manner to produce /C0 and /A0 respectively. On subse-uent hydrolysis of /C0 and /A0 gives optically active substances /G0 and /50. "oth /G0 and /50 on decarbo,ylation gives propanol+(. #dentify /A0, /"0, /C0, /A0, /G0 and /50

;.

/a0

/b0

ALDEHYDES & KETONES

60

/c0

/d0

K.

Zn I Hg ! HCl =roduct.

/a0

/b0

/c0

/d0

().

/a0

/b0

/c0

/d0

/b0

Addition of bisulfite 8 C ?O7 @a + C + @a + H?O7 8 88 OH O Example

Msed in purification /@ot for hindered Ketones0

"isulfite addition product

H 8 C = O + @a + H?O7
"en&aldehyde

H 8 C ?O7 @a + 8 OH

CH7 CH 7 8 8 CH 7 CH C CH CH 7 + @aH?O 7 no reaction 88 O

ALDEHYDES & KETONES

61

/c0

Addition of derivative of ammonia. 8 C + H ' @ N C @H N 88 8 O OH

C = @ N + H 'O

'sed for identification )(* G H ' @OH H ' @ @H ' H ' @ @H C: H 4 Hydro,ylamine Hydra&ine =henylhydra&ine ?emicarba&ide Product
> C = @ OH

O,ime Hydra&one =henylhydra&one ?emicarba&one

> C = @ @H ' > C = @ @HC: H 4 > C = @ @HCO@H '

H ' @ @H C @H ' 88 O @H@H ' 8 @O ' 8 @O '

', <+Ainitrophenyl hydra&ine

@H @ = C 8 @O ' 8 @O '

', < dinitrophenylhydra& one /bright orange or yellow precipitate used for identifying aldehydes and etones0

/d0

Addition of hydro,ylamine

CH 7 C = O + @H ' OH CH 7
/e0

CH 7 C = @ OH CH 7

Addition of Alcohols% Acetal 5ormation

H H 8 8 dry HCl R C = O + 'ROH HO R C OR + H 'O + 7 8 OR

An acetal /gem+diether0

ALDEHYDES & KETONES

62

+ #n H 7O , RCHO is regenerated because acetals undergo acid cataly&ed cleavage much more easily than do ethers. ?ince acetals are stable in neutral or basic media, they are used to protect the CH = O group.

Illustration

5ormation of o,imes and other ammonia derivatives re-uires slightly acidic medium ( pH = 4 : ) for ma,imum rate, while basic or more highly acid conditions lowers the rate. G,plain> #n the formation of o,imes of carbonyl compounds, it is often necessary to ad$ust the pH of the medium $ust to right acidity. #n the addition reaction a nucleophilic attac by basic nitrogen compound ta es place on the carbonyl carbon. =rotonation of carbonyl o,ygen ma es the carbonyl carbon more susceptible to nucleophilic attac . #n highly acidic conditions the nitrogen compound itself undergoes protonation.

Solution

)alo enation of Ketones O O 88 8 88 8 C C + H ' C C + HH 8 8 H H H ' = Cl ' , "r' , # ' /b0 Conversion to dihalides

/a0

== O + =Cl4 O 88 + ?5<
Acidity of + + )ydro ens

Cl Cl 5 5

+ =OCl7

+ ?O5'

Carbonyl group largely determines the chemistry of aldehydes and etones. "ut how the carbonyl group strengthens the acidity of hydrogen atoms attached to the + carbon and by doing this gives rise to a whole set of chemical reaction> 8 8 8 C C + . " C C + "H 88 8 88 H O O ( #)

ALDEHYDES & KETONES

63

Aldol Condensation ?ubstrate Reagent aldehyde or etone containing hydrogen dilute base ( commonly used ) , =roduct + hydro,aldehyde or + hydro,y etone

Mnder the influence of dilute base or dilute acid, two molecules of an aldehyde or etone may combine to form a + hydro,yl aldehyde or etone. The + carbonion generated by the base from one molecule of aldehyde. Or etone adds to the carbonyl carbon of the other molecule and the two molecules condense and form + hydro,yl aldehyde or etone. Cet us consider the mechanism for the OH catalysed aldol condensation of acetaldehyde . H 8 HO + H C CHO 8 H

CH ' CHO + H 'O

H ' C = CH O H
Key step in condensation

CH 7 C + CH ' CHO CH 7 CH CH ' CHO 88 8 O O

CH 7 CH CH ' CHO + H O H CH 7 CH CH ' CHO 8 8 O OH

+hydro,yaldehyde

Aldol condensations are reversible, and with etones the e-uilibrium is unfavourable for condensation product. + hydro,ycarbonyl compounds are readily dehydrated to give ++ unsaturated carbonyl compounds. 3ith Ar on + carbon, only dehydrated product is isolated. Crossed Aldol Condensation An aldol condensation between two different carbonyl compounds so called crossed aldol condensation 6 is not always useful as a mi,ture of four different possible products may be obtained.

ALDEHYDES & KETONES

64

Mnder certain condition, a good yield of a single product can be obtained from a crossed aldol condensation. One reactant contains no + hydrogens and therefore is incapable of condensation with itself /e.g. Aromatic aldehydes or formaldehyde0.

CH7CHO, ')

H H H 8 8 8 C = C C = O
Cinnamaldehyde Crossed Aldol Condensations

H 8 CH7COCH7 OH C = O ())

H H O 8 8 88 C = C C CH 7

C:H4COCH7

H H 8 8 C = C C 88 O CPP

((.

?how how each of the following compounds may be prepared from simple aldehydes or etones utili&ing aldol reaction.

O 88
/a0 /b0 CHO

/c0 OH

CHO

/d0

O 88

OH 8

('.

/a0

/b0

ALDEHYDES & KETONES

65

/c0

/d0 @one of these.

(7.

5ind the ma$or product of given reaction.

O 88 =h I CH == CH I CH I C IH ' /a0 O 88 /c0 CH7CH 'CH == CH I CH ' I C I H

O 88 CH 7CH ' I CH == C I C I H /b0 8 CH 7 O 88 /d0 =h I CH = = CICIH 8 CH 7

Reactions Related to the Aldol Condensation

Canni,,aro Reaction Aiscussion . #n the presence of concentrated al ali, aldehydes containing no + +hydrogens undergo self+ o,idation and reduction to yield a mi,ture of an alcohol and a salt of a carbo,ylic acid. This reaction is nown as Canni,,aro - reaction. Two successive additions are involved. /a0 /b0 Addition by hydro,ide ion in first step Addition of hydride ion in the ne,t step H H 8 8 Ar C = O + OH Ar C O 8 OH H O H O 8 8 8 88 Ar C = O + H C Ar Ar C H + HO C Ar 8 8 r.d.s. OH O H O 8 88 Ar C H + O C Ar 8 OH

/=roton e,change0

ALDEHYDES & KETONES

66

This e,plains the Crossed Canni&&aro reaction involving formaldehyde to ta e place in the way that it does. ArCHO + HCHO HCO ' @a + + ArCH 'OH On both electronic and steric grounds, the step ( is faster for HCHO. Hence becomes the hydride donor in the ne,t step. H H 8 8 H C = O + OH H C OH 8 O H H 8 8 Ar C = O + H C OH ArCH 'OH + HCO ' 8 O Illustration /i0 #n the presence of concentrated OH , aldehydes lac ing an + hydrogen undergo the Canni&&aro reaction. Nive the products of the reactions of /a0 ben&aldehyde /b0 trimethylacetaldehyde /c0 furaldehyde. /ii0 /a0 ?uggest a mechanism for the Canni&&aro reaction. Cabel the slow step. /b0 How does the mechanism account for the fact that the product alcohol contains no carbon+bound deuterium when the reaction is run is A ' O > Solution
/i0 /a0 =hCH ' OH + =hCOO /b0 2e7CCH ' OH + 2e7CCOO

/c0 O

CH ' OH +
O

COO

OH 8 R C O /ii0 /a0 R C = O + OH 8 8 H H
OH H OH H 8 8 8 slow /b0 R C O + R C = O R C = O + R C O RCOO + R I CH ' I OH H H

#n /b0 that was originally the aldehydic H is transferred /hydride transfer directly from the adduct anion to a second aldehyde molecule without any instrusion by solvent ( A ' O ) .

ALDEHYDES & KETONES

67

CPP (<. /i0 3hat are the products of the crossed+Canni&&aro reaction of /a0 H ' CO and =hCHO /b0 H ' CO and 2e7CCHO > /ii0 3hy is H ' CO always o,idi&ed in the crossed+Canni&&aro reactions in previous problem> /iii0 Nive the products of the Canni&&aro reaction of =hCOCHO /A0 and =hCOCHCl ' /"0 and e,plain their formation A Per#in Condensation
CH7COO@a CHO + ( CH 7CO ) ' O C: H 4CH = CH CO ' H

Acetic Anhydride

Cinnamic acid

H 8 =h C = O + CH 7 C H 7C C

O
OAc hydrolysis O

H H 8 8 =h C = C C
7+=henylpropenoic acid

OH O

Gster can be condensed with aromatic aldehydes in the presence of al o,ides% thus ben&aldehyde and ethylacetate in the presence of sodium etho,ide, give ethyl cinnamate, C: H 4CH = CHCOOC ' H 4 . H O 8 OGt C = O + CH 7 C OGt CH = CH C 88 OGt O H OH 8 8 =h C = O + CH ' C O Gt =h C CH CO ' Gt =h CH = CH CO ' Gt 88 8 8 O H H )alo enation of Ketones
H or OH C C + H ' % C C + HH 8 88 8 88 H O H O
+

H ' = Cl' , "r' , # '

Ketone

/a Halo Ketone0

ALDEHYDES & KETONES

68

Examples :

O + "r'
H+

+ H"r
"r

CH 7 CH 7 CH 7 8 8 8 OH CH7 C C CH 7 + # ' + OH CH 7 C C C#7 CH7 C CO ' + CH#7 8 88 8 88 8 CH7 CH 7 O CH 7 O

*ote : The Haloform Test depends upon the fact that the three hydrogens on the same carbon atom are successively replaced by halogen. Ta ing acetone as an e,ample we see that the carbon that suffers the initial substitution to the preferred site undergoes further substitution.

H H 8 8 HCCCH 8 88 8 H O H

OH

H 8 H 7C C C H 88 O H H 8 8 X HCCCH 88 8 O H

H 8 H 7C C = C H 8 O

@ot formed

Glectron withdrawal by halogen ma es hydrogens on the carbon to which halogen has already being attached more acidic and hence more readily removed by base to give further substitution.

R C CH 7 88 O

OH OH 8 8 OH R C CH 7 R C + CH 7 R CO ' + HCH 7 88 8 O O

Glectron withdrawal by three halogens ma es CH7 comparatively wea ly basic /for a carbanion0 and hence acts as a good leaving group.

Thus both essential aspects of the haloform reaction 6 regiospecificity of halogenation, and cleavage 6 are controlled by the factor% stabili&ation of a carbanion through electron withdrawal. Claisen Condensation/ Formation of 0 1 Keto Esters

ALDEHYDES & KETONES

69

An + hydrogen in an ester, li e an + hydrogen in an aldehyde or etone, is wea ly acidic, because, the carbonyl group helps to accommodate the negative charge of the carbanion. 3hen ethyl acetate is treated with sodium etho,ide, and the resulting mi,ture is acidified ethyl 7+ o,obutanoate, generally nown as ethyl acetoacetate or acetoacetate or acetoacetic ester is obtained.
C ' H4OH Gthyl acetate + sodium etho,ide ?odio+acetoacetic ester

/' moles0

H+ CH 7 C CH ' COOC' H 4 88 O Gthyl acetoacetate

( a, +Keto ester )

Gthyl accetoacetate is the ester of a + Keto acid% its preparation illustrates the reaction nown as the Claisen Condensation. O 88 /a0 CH 7 C OC' H 4 + OC ' H 4 C ' H 4OH + CH 'COOC 'H 4 /b0 O O 88 8 CH 7 C OC ' H4 + CH 'COOC ' H 4 CH 7 C CH 'COOC ' H 4 8 OC' H 4 O 88 CH 7 C CH ' COOC' H 4 + OC' H4 /c0 O 88 CH 7 C CH ' COOC ' H 4 + OC ' H 4 CH 7COCHCOOC ' H 4 + HOC ' H 4
?tronger acid ?tronger "ase 3ea er "ase 3ea er acid

Crossed Claisen Condensation Examples :

OC' H4 CO' C' H4 + CH 7CO ' C ' H 4

Gthyl ben&oate

Gthyl acetate

Gthyl ben&oyl acetate

C CH ' COOC ' H 4 + C' H 4OH 88 O

ALDEHYDES & KETONES

70

Ketones /but not aldehydes0 undergo a crossed Claisen Condensation with ester. Example :
@aOC' H4 CH7COOC' H 4 + CH 7COCH 7 CH 7COCH 'COCH 7 + C 'H 4OH

Gthyl acetate

Acetone

Acetylacetone

!ecarboxylation of 0 1 Keto Acids + Keto esters are normally prepared by Claisen Condensation. Hydrolysis of the + eto ester gives the + eto acids which are very easy to decarbo,ylate simply by heating. Aecarbo,ylation of free acetoacetic acid involves transfer of the acidic hydrogen to the eto+group followed by loss of carbon+dio,ide via a cyclic :+membered T.?. CH '

CH 7 C 88 O

C=O 8 H O

CH 7 C = CH ' + CO ' 8 OH CH 7 C CH 7 88 O

(. H 'O ' OH (. @aOGt 'CH 7CO ' Gt CH 7 C CH 'CO ' Gt CH 7 C CH 'CO ' H '. H + '. H D 88 88 O O

/Aecarbo,ylation0

O 88

CO ' CO ' H

CH 7 COCH 7 + CO ' O 88

Addition of Ammonia Aldehydes react with ammonia to form aldehyde ammonia

R H C = O + @H 7

R C H

OH @H '

Aldehyde ammonia

The aldehyde ammonia is unstable and lose water immediately to form aldimine. The dehydration product is not usually obtained because, in most cases, it immediately polymerises to form cyclic trimers.

ALDEHYDES & KETONES

71

CH 7 H

C = O + @H 7

CH 7 C H

OH @H '
H'O

CH 7 H

C = @H

Aldehyde ammonia /unstable0

Aldimine /very reactive0

CH 7 3hen treated with ammonia, formaldehyde does not form an aldehyde 6 ammonia, but gives instead C = @H @H 7 polymerisation he,amethylenetetramine, used in medicine as a+urinary antiseptic under the name Mrotoropine. H :HCHO + <@H 7 ( CH ' ) : @ < + 4H 'O ( ;)O ) @ 8 CH ' 8 @ CH ' CH '
He,amethylene tetramine

CH '

CH ' CH '

Ketones also give etone+ammonia but these cannot be isolated. Acetone reacts slowly with ammonia to form acetone ammonia and then a comple, compound.

CH 7 CH 7

C = O + @H 7

low temp

CH 7 C CH 7

OH @H '

Acetone ammonia

Acetone upon treatment with ammonia at higher temperature give acetoneammonia.

CH 7 ' CH 7

C = O + @H 7

low temp

CH 7 C CH 7

CH 'COCH 7 @H '

diacetone ammonia

Aldimines, ?chiffLs bases or a&omethines are formed when aldehydes react with aliphatic primary amines, which is removed by slow distillation. 2eer3ein - Ponndorf - 4erley Reduction

ALDEHYDES & KETONES

72

The carbonyl compound is heated with aluminium isopropo,ide in isopropanol solution, the isopropo,ide is o,idised to acetone, which is removed by slow distillation. dil R ' CO + R 'CHOH H ?O ( CH 7 ) ' CHO ) Al ] ( R 'CHO ) 7 Al + CH 7COCH 7
7
' <

The reducing agent is specific for the carbonyl group, and so may be used for reducing aldehydes and etones containing some other functional group that is reducible e.g., a double bond or a nitro group.

H R 'C O Al
+

H C 2e ' O O Al O
H+

R 'C

C 2e '

R ' CH + O Al

2e' C O

H R ' CH OH + 2e 'CO

Pinacol1Pinacolone Rearran ement /(, '+methyl but 6 (, ' diol0 upon treatment with hot dil. H '?O < , pinacol undergoes a rearrangement and dehydration to give a methyl etone.

CH 7 CH7 8 8 H7C C C CH 7 H C C C CH H O + H C C C ( CH 7 ) 7 ( 7)' ' ( 7 )' 7 8 8 8 8 8 + OH OH OH OH ' OH CH 7 8 CH 7 C C CH 7 88 8 O CH 7

5ischen#o Reaction All aldehydes can be made to undergo the Canni&&aro reaction by treatment with aluminium etho,ide. Mnder these conditions the acids and alcohols are combined as the ester, and the reaction is then nown as the Tischen o reaction% e .g., acetaldehyde gives ethyl acetate, and propionaldehyde gives propyl propionate.

ALDEHYDES & KETONES

73

'CH7CHO + Al ( OGt ) 7 CH 7C OGt + Al ( OGt ) 7 88 O )ydrolysis CH7 C OH + GtOH 88 O

Formaldehyde/ 2ethanal/ )1C)6& Preparation (.

"y the reduction of carbon mono,ide 5ormaldehyde is produced from carbon+mono,ide when a mi,ture of these gases /water gas0 is passed at low pressure through an electric discharge of low intensity. O 88 CO + H ' H C H "y o,idation of methyl alcohol+large -uantities of formaldehyde are prepared by passing a mi,ture of methyl alcohol vapour and air over heated copper or silver. O 88 ( CH 7OH + O ' H C H + H 'O '
5ormaldehyde

'.

A catalyst composed of molybdenum trio,ide and ferric o,ide Converts K4O of methyl alcohol to formaldehyde. #n the o,idation method, the condensate obtained is a mi,ture of formaldehyde, methanol and water. #t is freed from e,cess of methanol by distillation, and the resulting mi,ture is nown as formalin /<)O formaldehyde, ;O methanol, 4'O water0. Polymers of Formaldehyde /i0 #n dilute a-ueous solution, formaldehyde is almost ())O hydrated to form methylene glycol this is believed to be the reason for the stability of dilute formaldehyde solutions. CH 'O + H 'O CH ' ( OH ) ' /ii0 3hen formaldehyde solution is evaporated to dryness, white crystalline solid, m.p.+('(+('7*C, is obtained this is nown as paraformaldehyde, ( CH ' O ) n.H ' O, and it appears to be a mi,ture of polymers, having values between : and 4). =araformaldehyde reforms formaldehyde when heated.

/iii0 3hen formaldehyde gas is allowed to stand at room temperature formaldehyde gas slowly polymerises to a white solid, trio,ymethylene ( CH ' O ) 7 , mp :(+:'*C. Trio,an is prepared by distilling formaldehyde solution /:)O0 containing a little sulphuric acid. This trimer is soluble in water and does not show any reducing properties. Condensation Reactions of Formaldehyde

ALDEHYDES & KETONES 5ormaldehyde can participate in a crossed Canni&&aro reaction. C: H 4CHO + HCHO + @aOH C: H 4CH 'OH + HCO ' @a Aldehydes with one + hydrogen atom reacts as follow .

74

CH 'OH
@aOH R(R 'CHCHO + HCHO R R 'CH

?imilarly,

CHO
@aOH RCH ' CHO + HCHO RCH

CHO
HCHO

CHO RC CH 'OH CH 'OH

CH ' OH CH ' OH R C CH ' OH + HCO ' @a CH ' OH

HCHO @aOH

( ) CH 7CHO + <CH 'O C ( CH 'OH ) < + ( HCO ' ) ' Ca

Ca OH

Acetaldehyde/ $Ethanal% C) 7 C) = & Acetaldehyde /ethanal0 is prepared industrially . /i0 /ii0 "y the dehydrogenation or air o,idation of ethanol in the presence of silver catalyst at 7))*C.
Ag air CH 7CHO + H ' CH 7CH 'OH CH 7CHO + H 'O Ag

"y passing a mi,ture of ethylene and o,ygen, under pressure, into an a-ueous solution of =d and cupric chlorides at 4)*C. CH ' = CH ' + =dCl ' + H 'O CH 7CHO + =d + 'HCl 'CuCl' + =d 'CuCl + =dCl ' ( 'CuCl + 'HCl + O ' 'CuCl ' + H 'O ' Acetaldehyde is a colourless, pungent smelling li-uid, b.p, '(*C.

Polymers of Acetaldehyde 3hen acetaldehyde is treated with a few drops of conc. H '?O < , a vigorous reaction ta es place and the trimer paraldehyde, ( CH7CHO ) 7 is formed. #tLs structure is believed to be /#0. Chloral /CCl 7 C) = &0 Chloral /trichloroacetaldehyde0 is prepared industrially by the chlorination of ethanol. Chlorine is first passed into cold ethyl alcohol and then at :)* till no further absorption of chlorine ta es place. The final product is chloral

CH7 8 CH O 8 H 7C CH
O ( #) O 8 CH CH 7

ALDEHYDES & KETONES

75

alcoholate which separates out as a crystalline solid. This on distillation with concentrated H '?O < gives chloral. CH 7CH ' OH + Cl ' CH 7CHO OH OH 7Cl' CH 7CHO + HO C ' H CH 7 CH CCl7 CH 7HCl OC' H4 OC' H4 hemiacetal Conc. Reaction with Al alis . with conc. KOH, it yields pure chloroform. CCl7CHO + C ' H 4O?O7H O O O 88 8 88 CCl7C H + OH CCl7 CH OH CCl 7 + H C OH
H 'O H '?O <

CHCl7
#n acids, most aldehydes form no nisolable unstable gem+diols but chloral hydrate is stable.

OH Cl7CCH OH Cl 8 + + + Cl C C = O + H 'O 8 8 Cl H
Cl OH 8 8 Cl C C OH 8 8 Cl H

H Cl O Cl C C H Cl H O

repulsion from adjacent + ve charges chloral hydrate less +repulsion

strong electron withdrawing group on a + C destabili&es an ad$acent carbonyl group because of repulsion of ad$acent positive charges. Hydrate formation overcome the forces of repulsion. 8en,aldehyde "en&aldehyde /and aromatic aldehydes in general0 resemble aliphatic aldehydes in the following reactions . /i0 /ii0 #t gives the ?chiffLs reaction. #t is readily o,idi&ed, i.e. it is a strong reducing agent . e.g. it reduces ammoniacal silver nitrate to silver, itself being o,idi&ed to ben&oic acid. "en&aldehyde o,idi&es to ben&oic acid when e,posed to air. #t does not reduce 5ehlingLs solution.

"en&aldehyde differ from aliphatic aldehydes in following ways . /i0

ALDEHYDES & KETONES /ii0

76

#t does not readily polymerise e.g. it does not resinify with @aOH, but undergoes canni&&aro reaction. "en&aldehyde may be prepared by any of the following methods, which are general for its homologues as well.

(.

"y hydrolysis of ben&ilidene chloride with a-ueous acid /this is also a commercial method0. C: H 4CHCl' + H 'O C : H 4CHO + 'HCl

'.

"en&aldehyde may be conveniently prepared in the laboratory by o,idising toluene with CrO7 in acetic anhydride. As the ben&aldehyde is formed, it is converted into ben&ilidene acetate, thereby preventing further o,idation of the ben&aldehye. Hydrolysis of the acetate with dilute sulphuric acid or hydrochloric acid gives ben&aldehyde.
CrO7 H C: H 4CH7 C: H 4CH ( OCOCH 7 ) ' C : H 4CHO + 'CH 7CO 'H ( CH7CO ) O
+ '

A better yield of ben&aldehyde may be obtained by o,idising ben&yl alcohol with CrO7 in acetic anhydride. An interesting o,idising agent is chromyl chloride $Etard9s reaction%. #n this method toluene is treated with chromyl chloride in CCl < solution and the comple,, which is precipitated is decomposed with water.
H 'O C: H 4CH 7 + 'CrO ' Cl ' C: H 4CH ( OCrCl 'OH ) ' C : H 4CHO

Gatterman1Koch Aldehyde Synthesis : "en&aldehyde may be synthesi&ed by bubbling a mi,ture of carbon+mono,ide and hydrogen chloride through a solution of either nitroben&ene or solution containing ben&ene and a catalyst of AlCl7 and small amount of cuprous chloride.
AlCl7 C: H : + CO + HCl C: H 4CHO + HCl

The mechanism of this reaction is uncertain, but it appears li ely that the formyl cation is the active species. CO + HCl + AlCl7 CH = O H C O + + AlCl < #t also appears li ely that the cuprous chloride forms a comple, with the CO, thereby increasing its local concentration. 5he Gatterman1Koch aldehyde synthesis is not applicable to phenols and their ethers, or when the substituent is strongly deactivating e.g. nitroben&ene. Gattermann Aldehyde Synthesis :

ALDEHYDES & KETONES

77

3hen ben&ene is treated with a mi,ture of HC@ and HCl in the presence of AlCl7 , and then comple, so produced decomposed with water, ben&aldehyde is produced.
AlCl7 H'O C: H : + HC@ + HCl C : H 4CH = @H HCl C: H 4CHO + @H 7

Sommelet9s Reaction : "en&aldehyde is produced when ben&yl chloride is reflu,ed with he,amethylenetramine in a-ueous ethanolic solution followed by acidification and steam distillation. C: H 4CH ' Cl + ( CH ' ) : @ < C: H 4CHO 8en,oic Condensation : 3hen reflu,ed with a-ueous ethanolic potassium cyanide ben&aldehyde forms ben,oin.
KC@ 'C: H 4CHO C: H 4CHOHCOC : H 4

O 88 C: H 4C + C@ 8 H

O 8 C: H 4 C C@ 8 H

OH 8 C: H4 C C@

C: H 4CHO

OH O 8 8 C: H 4 C C C: H 4 8 8 C@ H

O OH 8 8 C: H4 C C C: H4 8 8 C@ H

O OH 88 8 C: H4 C C C: H4 + . C@ 8 H
Analysis of Aldehydes and Ketones Aldehydes and etones are characteri&ed through the addition to the carbonyl group of nucleophilic reagents, especially derivatives of ammonia. All aldehyde or etone will, for e,ample react with ',<+dinitrophenylhydra&ine to form an insoluble yellow or red solid. Aldehydes are characteri&ed, and in particular are differentiated from etones through their ease of o,idation . aldehydes give a positive test with TollenLs reagent% etones do not.

ALDEHYDES & KETONES

78

Aldehydes are also, of course, o,idi&ed by many other o,idi&ing agents . by cold, dilute, neutral K2nO < and by CrO7 in H '?O < . A highly sensitive test for aldehydes is the ?chiffLs test. Aldehydes and etones are generally identified through the melting points of derivatives li e ',<+ dinitrophenylhydra&ones, o,imes, and semicarba&ones. 2ethyl Ketones are characteri&ed through the iodoform test. Aldehydes can be o,idised by 5ehlingLs solution. 5ehlingLs solution, an al aline solution of cupric ion comple,ed with tartarate ion /or "enedicts solution, in which comple,ing is with citrate ion0% the deep+blue colour of the solution is discharged, and red cuprous o,ide precipitates. 5ehlingLs solution is made by mi,ing65ehling A solution, which contains copper sulphate, D 5ehling " solution, which contains sodium hydro,ide and Rochelle salt /?odium =otassium Tartarate0. Auring the o,idation of aldehydes to acids, the cupric ions are reduced to cuprous ions which are precipitated as red cuprous o,ide.
+ RCHO + 'Cu '+ + 7 OH R CO ' + 'Cu 'H 'O

'Cu + + ' OH Cu 'O + H 'O

Illustration

Cuprous o,ide /red0

An al ene C: H(' , after o&onolysis gives two products one of these gave a positive iodoform reaction but a negative TollenLs test. The other product gave a positive TollenLs test but a negative iodoform test. #dentify the al ene. One product is methyl etone as it gives positive iodoform test while the other product is an aldehyde. The aldehyde does not have methyl group as it does not respond to iodoform test. Hence the product of o&onolysis are CH7COCH 7 and CH 7CH 'CHO.

Solution

CH 7 CH 7

C = CHCH 'CH 7

'+2ethyl pentene+'

CPP

(4.

/a0

/b0

ALDEHYDES & KETONES

79

/c0

/d0

(:. #dentify name of reaction. /a0 Aldol condensation /c0 Crossed Claisen condensation (9. /b0 Canni&&aro condensation /d0 Tischen o Reaction.

/a0

/b0

/c0

/d0

ALDEHYDES & KETONES

80

ANSWER TO CPP
(

O 88

O 88

H+

This etone is more acidic because the resulting enolate ion obeys Huc elLs rule and thus more stable. ' /a0 Cu or CuO,
+ /b0 K ' Cr' O9 , H

/c0 =.C.C. or Ag ' O 7 /A0 /"0

/C0 C: H 4CH ' CH 'C CC : H 4 <. 4. :. 9 C " " /a0 CH 7CH 'CHO /c0 CH 7CH 'CH ( OH ) C@ /e0 CH 7CH 'CH ( OH ) COOH /b0 CH ' = CHCH 'OH /d0 CH7 CH ( C@ ) CH ' OH /f0 CH 7 CH ( COOH ) CH ' OH

( Optically active )

( Optically active )

;. K. (). ((.

A A C /a0

O 88 + H

O 88
a- KOH

O 88

CH 8 OH

O 88
( ' )
H O

CH 7 8 ( H'O ) a- KOH /b0 'CH 7CH ' CHO CH 7 CH ' CH CH CHO CH 7CH ' CH = C CHO 8 8 OH CH 7

ALDEHYDES & KETONES

81

CH 7 8 /c0 'CH 7 CH CHO

a-. OH ( ?elf aldol )

CH 7 8 CH 7 CH CH C CHO 8 8 8 CH7 OH CH 7

/d0 CH 7CH ' C CH ' CH 7 88 O

?odium dimethyl amide or Cithium amide diisopropyl

OH 8 CH7CH ' CHO CH 7 CH ' C CH CH 7 CH 7 CH ' C CH CH CH ' CH 7 88 88 8 O O CH 7

/only one product0

Totally convert any of the aldehydes to the carbanion by using strong base, followed by reaction with the other aldehyde. This is done to avoid multiple products. ('. (7. (<. A A
/i0 /a0 =hCH ' OH + HCOO and /b0 2e7CCH 'OH + HCOO .

/ii0 ?ince H ' CO is the most reactive aldehyde, it e,ists in a-ueous OH solution mainly as the con$ugate base of its hydrate, H ' C ( OH ) O . There is also a statistical factor, because H ' CO has two HLs available for transfer in step /'0 of pervious problem, the other aldehyde hydrate anion has only one. /iii0These are internal crossed+Canni&&aro reactions. "oth A and " give =hCH ( OH ) COO . #n ", prior al aline hydrolysis gives compound A. The CHO is o,idi&ed because it has the aldehydic H needed for hydride transfer. Keto+groups can only be reduced, not o,idi&ed, in crossed+Canni&&aro reactions. (4. (:. (9. " C A

ALDEHYDES & KETONES

82

SOLVED SUBJECTIVE PROBLEMS

Problem : A etone A which undergoes a haloform reaction gives compound " on reduction. " on heating with sulphuric acid gives compound C, which forms mono+o&onide A. The compound A on hydrolysis in presence of &inc dust gives only acetaldehyde. #dentify A, " and C. 3rite down the reactions involved. 3e are given that
reduction A " H '?O< " C

Solution

C forms mono+o&onide, A
H ' O ! 1n A CH 7CHO

The compound A gives a haloform reaction% it must contain CH 7CO group. The compound C contains a double bond as it forms mono+o&onide A. ?ince, the compound A on hydrolysis gives only CH 7CHO, the structure of C would be CH7CH = CHCH 7 '+butene
( C)

The compound C is obtained by dehydration of ", thus the latter should be CH 7 CH CH ' CH 7 8 OH '+butanol
( ")

5inally, " is obtained by the reduction of A. Hence, the compound A should be CH 7 C CH ' CH 7 88 '+butanone O
( A)

The e-uations involved are as follows .

[ ] CH 7 C CH ' CH 7 CH 7 CH CH ' CH 7 88 8 O OH ( A) ( ") O
H

H '?O < H 'O

1n ! H 'O 'CH 7CHO

Problem (

CH7 CH 8 O

( A)

O7 CH CH7 CH 7 CH = CH CH 7 8 ( C) O

An organic compound A on treatment with ethyl alcohol gives a carbo,ylic acid " and compound C. Hydrolysis of C under acidic conditions gives " and A. O,idation of A with K2nO < also gives ". The compound " on heating with Ca ( OH ) ' gives G /molecular

ALDEHYDES & KETONES

83

formula C7H : O 0. G does not give TollenLs test and does not reduce 5ehlingLs solution but forms a ', <+dinitrophenylhydra&one. #dentify A, ", C, A and G. Solution The given reactions are as follows.
C ' H4OH A " H C "
+

/Carbo,ylic acid0

C A

+ K2nO <

' " C 7H : O

Ca ( OH )

( G)

The compound G must be etonic compound as it does not give Tollens test and does not reduce 5ehlingLs solution but forms a ', <+dinitrophenyl+hydra&one. Therefore, its structure would be CH 7COCH 7 /acetone0. ?ince G is obtained by heating " with Ca ( OH ) ' , the compound " must be CH 7COOH /acetic acid0. ?ince " is obtained by o,idation of A with K2nO < , the compound A must be an alcohol with molecular formula CH 7CH 'OH /ethanol0. ?ince " and A are obtained by acid hydrolysis of C, the compound C must be an ester CH7COOC' H 4 /ethyl acetate0. ?ince the compounds " /acetic acid0 and C /ethyl acetate0 are obtained by treating A with ethanol, the compound A must be an anhydride ( CH7CO ) ' O /acetic anhydride0. The given reactions are
acetic anhydride /A0
C H OH CH 7COOH ( CH7CO ) ' O
' 4

+ CH 7COOC' H 4
ethyl acetate /C0

acetic acide /"0

H+

Ca ( OH ) '

CH 7COCH 7
acetone /G0

CH 7COOH + C' H 4OH

acetic acid /"0 ethanol /A0

K2nO <

Problem 7

Two moles of an ester A are condensed in the presence of sodium etho,ide to give a + eto ester, ", and ethanol. On heating in an acidic solution, " gives ethanol and a + eto acid, C. On decarbo,ylation C gives 7+pentanone. #dentify A, " and C with proper reasoning.

ALDEHYDES & KETONES Solution

84

The reaction of ' mol of an ester giving + eto ester and alcohol in the presence of sodium etho,ide is nown as Claisen condensation. Cet the given reactions may be depicted as shown in the following.
OC ' H4 RCH ' C OR + RCH ' C OR 88 88 O O

( A)

( A)

R CH ' C CH C OR + R OH 88 8 88 O R O
+ eto ester /"0 ethanol
+

H R CH ' C CH C OH + R OH R CH ' C CH C OR heat 88 8 88 88 8 88 ethanol O R O O R O

+ etoacid /C0

R CH ' C CH C OH 88 8 88 O R O
5rom these reactions, it is obvious that R CH ' CH 7 R CH 7 Hence, the compounds A, " and C are A . CH 7CH 'C OCH 'CH 7 88 O " . CH7CH ' C CH C OC ' H 4 88 8 88 O CH7 O

heat R CH ' C CH ' 88 8 O R

C . CH 7CH 'C CH COOH 88 8 O CH 7

Problem ; An organic compound A ( C: H() ) on reduction first gives " ( C: H(' ) and finally C ( C: H(< ) . Compound A on o&onolysis followed by hydrolysis gives two aldehydes 5 ( C< H;O ' ) . Aetermine the structures of the compounds A to 5 with reasoning. Solution A ( C' H < O ) and G ( C' H ' O ' ) . O,idation of " with acidified K2nO < gives the acid

?ince o&onolysis of A gives two aldehydes, the compound A contains the carbon+carbon double bond. #n fact, the molecule of A contains two double bonds as it is successively o&onoly&ed products will remain same as in the compound A. Hence, it may be concluded

ALDEHYDES & KETONES

85

that the o&onolysis product include two molecules of A ( CH 7CHO ) and one molecule of G/OHC CHO0. 5rom this, we derive the structure of A as shown in the following.
O7 CH 7CHO + OHC CHO + OHCCH 7 CH 7CH = CH CH = CHCH 7

( A)

( G)

( A)

', <+he,adiene ( A)

The structure of " and C are as follows.

H' CH7CH = CHCH = CHCH7 CH 7 CH 'CH ' CH = CHCH 7 '+he,ene ( ")

H'

CH 7CH ' CH ' CH ' CH 'CH 7

O O 88 88 K2nO < CH 7CH 'CH 'CH = CHCH 7 CH 7CH 'CH ' C OH + CH 7C OH
"utanoic acid /50

The structure of 5 is as follows.

he,ane ( C)

Problem <

An organic compound A ( C: H(' O ) forms an o,ime but does not reduce TollenLs reagent. A on reduction with sodium+amalgam forms an alcohol " which on dehydration forms chiefly a single al ene C. The o&onolysis of C produces A and G. The compound A reduces Tollens reagent but does not answer iodoform test. 3hat are the structures of the above compounds> G,plain the reactions. The compound A must be a etone as it forms o,ime but does not reduce TollenLs reagent. The compound A must be an aldehyde. #ts structure does not include the fragment CH 7C 88 as it does not answer iodoform test. O The compound G must be a etone containing CH7C fragment. 88 O Cet the compounds A and G be RCH ' CHO and R COR , respectively, where R, R and R are all al yl groups. 5rom these, we get R R O7 RCH ' CH = C RCH ' CHO + O = C R R /A0 /G0 /C0 H 'O R R [ H] RCH ' CCH RCH 'CH CH 88 8 R R O OH
( A) ( ")

Solution

?ince the molecular formula of A is C: H(' O, it follows that R = R = R = CH 7 . Hence, the structures of molecules /A0 to /G0 and the reactions are as follows.

ALDEHYDES & KETONES

86

CH 7 CH 7CH ' CCH 88 O

/A0

CH 7CH ' CHCH 8 CH 7 OH

/"0 alcohol

[ H]

CH 7 CH 7 H 'O CH 7

5orms o,ime but does not reduce Tollens reagent

O7

CH 7CH 'CHO + CH 7COCH 7 CH 7CH 'CH = C

/A0 Reduce Tollens reagent but no iodoform test /G0 Aoes not reduce Tollens reagent but gives iodoform test /C0

CH 7

Problem =

A compound A reduces 5ehlingLs solution and gives positive silver mirror test. On warming with dilute al ali, followed by dehydration it gives a product " which also responds to both the above tests. #n addition, it decolourises the colour of bromine water. On treatment with hydrogen in the presence of nic el under pressure the compound " is converted to C which does not give any one of the above three test. 2olar mass of the compound C is 9< g mol(. Aeduce the structures of A and " giving the chemical e-uations involved. The compound A must be an aldehyde as it reduces 5ehlingLs solution and gives positive silver mirror test. The compound A also contains + hydrogen atom as it undergoes aldol condensation, the dehydration of which gives ". The latter contains unsaturation as bromine water is decolourised. Cet the structure of A be RCH ' CHO. The reactions involved are
@aOH RCH ' CHO + H 'CCHO RCH ' CH CH CHO 8 8 8 R OH R

Solution

H 'O RCH ' CH = C CHO 8 /"0 R

The reduction of " with H ' ! @i under pressure would be
H ' ! @i RCH 'CH = CCHO RCH ' CH 'CHCH 'OH 8 8 R R

( C)

?ince the molar mass of C is 9< g mol( , R in the compound C must be hydrogen atom. Hence, the structures of A, " and C are. A CH 7CHO " CH7CH = CHCHO C CH 7CH 'CH 'CH 'OH

ALDEHYDES & KETONES Problem > 3hen R glyceraldehydes, CH ' OHCH ( OH ) CHO is treated with cyanide and the resulting product is hydrolysed, two monocarbo,ylic acids are formed. These acids are identical with the acids obtained by H o,idation with "r' + water of ( ) threose and ( ) erythrose. Assign single structure to ( ) erythrose and to ( ) threose. Solution
H
CHO
C@ , H + H OH H CH 'OH

87
CHO OH

CH 'OH C@

C@ OH + HO OH H

H OH CH 'OH H + , H 'O

CH ' OH H + , H 'O

CHO

COOH OH OH HO H

COOH
"r' ,H ' O H HO OH H

CHO

H H

"r' H 'O OH H OH H

H OH
/ 0 Threose

/ 0 Grythrose

CH 'OH

CH 'OH

CH 'OH

CH 'OH

@ote . The erythro isomer is the one that is convertible /in principle at least0 into a meso structure, whereas the threo isomer is convertible into a racemic modification. The names of these compounds are the basis for designations erythro and threo acid to specify certain configuration of compounds containing two chiral carbons. Problem ? How starting from /# and ##0, one can get /###0, <, <+dimethyl+'+cyclohe,anone0 O 88
2e ' CHCHO ( #) H ' C = CHCOCH 7 ( ## )

###

Solution

The first reaction is the 2icheal addition of the enolate anion to methyl vinyl etone followed by intra molecular condensation. O O 88 88 H ' C = CH COCH 7 + H CH 7 CH7 CHO CHO 2e ' C CHO a con$ugate aldol addition /2ichael addition0 O O 88 88
OH Aldol condensation

CH ' CHO

O 88
( )
i HD

ALDEHYDES & KETONES Problem :@

88

An ester /A0 is condensed in the presence of sodium metho,ide to give a + eto ester /"0 and 2ethanol. On mild hydrolysis with cold conc. HCl, /"0 gives methanol and 7+o,o+ acid /C0. /C0 underwent readily decarbo,ylation to give cyclopentanone. /a0 #dentify /A0, /"0 and /C0 /b0 @ame the reaction involved in conversion of /A0 to /"0 /c0 Nive the mechanism of decarbo,ylation

Solution

/a0

O2e
O O
@aO2e

=== O + 2eOH CO ' 2e

( A)

O2e
O 88
7
(

+ etoester ( ")

CO ' H
'

( " )
mild Hydrolysis

+ 2eOH

7+o,o acid or + eto acid

O 88

( C )
CO '

+ CO '

/b0 Aie mann condensation /intramolecular Claisen ester condensation0 /c0 2echanism of decarbo,ylation

C=O O 8 H

CO'

enol

OH

eto

ALDEHYDES & KETONES

89

SOLVED OBJECTIVE PROBLEMS

Problem :
@aOH, == O ( aldol ) A

O 88
/a0

===

/b0

===

=== O

/c0 Solution a

===

/d0

== O
H at C ta es part which is condensed to carbonyl group of second molecule% heating causes , elimination. Problem ( /a0 Canni&&aro 'CA ' = O + OH H and P /P is alcohol, A is deuterium0 H and P will have structure . O A 88 8 /a0 A C O , A C OH 8 A O A 88 8 /b0 A C O , A C OH 8 H

Solution

O A 88 8 /c0 O C O , A C OH /d0 none is correct 8 A c A A A A A 8 8 8 + A C O A C = O + OH O C A + C = O O=C 8 8 A OH OH A

=roton transfer

A O=C O +

A 8 A C OH 8 A

ALDEHYDES & KETONES /c0 Problem 7

O 88 H7O + CH 72g"r + CH ' = CH C H H. H is

90

OH 8 /a0 CH ' = CH C H 8 CH 7 /c0 CH 7 CH ' CH ' CHO Solution

/b0 CH ' CH = CH CH 7 8 CH7 /d0 none is correct

O 88 CH ' = CH C H is con$ugate system #

OH 8 H 7O + CH 7 CH ' CH = C H hence # + CH 7 2g "r

tautomerises

O 88 CH7 CH ' CH ' C H

/c0

O
Problem ; A is /a0
Hg?O < ! H '?O < C CH A

O C CH 7 88 O O CH ' COOH
/b0

O CH ' CHO OH
/d0

/c0 Solution b

CH ' CHO

C = O is /G3N0 hence electron transfer is onwards ring. O

C CH
/b0

ALDEHYDES & KETONES Problem < Gnd product of the following se-uence of reactions is CH7 2g"r CO ' ! H7O + Hg?O< ! H '?O < Ag ' O CH CH O 88 /a0 CH 7 C COOH /b0 CH ' ( COOH ) ' O O 88 88 H C CH 'COOH /c0 CH 7 C CHO /d0 b

91

Solution

CH CH + CH 72g"r CH C 2g"r
CO ' ! H 7 O
D

COOH is ( G3N )

CH C COOH
Hg?O < ! H '?O <

OHC CH ' COOH

Ag ' O

HOOC CH ' COOH

/b0 Problem =

O
(. K"rO, COCH7 A '. H D

CH 7 O
/a0

7.

O
/b0

COOH CH 7

CH7

/c0 Solution b

COOH OH

/d0

COOH CH 7 OH O CH 7

#ntermediate is O

COOH which decarbo,ylates to CH 7

/when + eto acid is heated, CO ' is lost0 /b0

ALDEHYDES & KETONES

O 88 ?eO' CH 7 C CH 7 A

92

Problem >

A will . /a0 reduce Tollens reagent /c0 form dio,ime Solution a/ b/ c and d ?eO ' o,idises CH ' w.r.t. eto group Problem ? /a0, /b0, /c0 and /d0 @aOH 7HCHO + CH 7CHO A. A can /a0 reduce TollenLs reagent /c0 react with @a Solution a/ b/ c and d A is by aldol condensation CH ' OH 8 HOH ' C C CHO 8 CH ' Problem A /a0, /b0, /c0 and /d0 3hen aldehyde is heated with 5ehlingLs solution, it gives a precipitate of /a0 Cu /c0 Cu ' O Solution c Copper ?ulphate is reduced to Cu ' O Problem :@ /c0 Aldol condensation is not given by /a0 CH 7CHO Solution d 5ormaldehyde does not have alpha hydrogen atom Problem :: Solution /d0 3hich of the following gives positive iodoform test and positive 5ehilingLs solution test> /a0 acetone b /b0 acetaldehyde /c0 ethanol /d0 formaldehyde /b0 CH7COCH 7 /c0 CH 7CH 'CHO /d0 HCHO /b0 CuO /d0 Cu + Cu 'O + CuO /b0 give Canni&&aro reaction
' + /d0 give green colour with Cr' O9 ! H

/b0 give iodoform test /d0 give Canni&aro reaction

ALDEHYDES & KETONES Acetaldehyde has CH7CO group as well as CHO group. Problem :(

93

/b0 The best o,idising agent for o,idation of CH 7CH = CHCHO to CH7CH = CH COOH is /a0 acidified K2nO < /c0 acidified K ' Cr' O9 /b0 al aline K2nO < /d0 Ag ( @H7 ) '
+

Solution

d A is a specific o,idising agent /d0 The most appropriate reagent for the conversion of '+pentanone to butanoic acid is /a0 sodium hypoiodite /c0 acidified K2nO < /b0 O ' /d0 al aline K2nO <

Problem :7

Solution

a Haloform reaction converts methyl etones to acids directly /a0 3hich of the following will react at the slowest rate with a nucleophile /a0 methanal /b0 butanone /c0 '+pentanone /d0 7+pentanone d #f the electrophilic character of carbon is considerably reduced, then the reaction will be slow.

Problem :; Solution

Problem :<

/d0 3hich of the following are e,amples of aldol condensation>

dil. @aOH CH 7CHOHCH 'CHO /a0 'CH7CHO dil. @aOH CH 7C ( OH ) ( CH 7 ) CH 'COCH 7 /b0 'CH7COCH 7 dil. @aOH CH 7OH /c0 'HCHO dil. @aOH C: H 4CH ' OH /d0 C: H 4CHO + HCHO

Solution

a/ b Aldol condensation is the condensation of carbonyl having + hydrogen /a0, /b0

ALDEHYDES & KETONES

94

EXERCISE I
C8SE PR&8BE2S (. '. Nive the #M=AC name of OHC

CHO, CH 7CH = CHCHO, CH 7COCH 'COCH 7 .

An organic compound with molecular formula, CK H() O forms ', <6A@= derivative, reduces TollenLs reagent and undergoes Canni&&aro reaction. On vigorous o,idation, it gives (, '6ben&ene dicarbo,ylic acid. #dentify the reactant. @ame two methods which are commonly used to convert

7. <.

C = O into a

CH ' group.

A chemical compound is represented by the formula C7H : O. Nive one chemical test to show that the compound is an aldehyde and not a etone. 3hy does not this compound give Canni&&aroLs reaction> Nive possible e,planation for each of the following /i0 cyclohe,anone forms cyanohydrin in good yield but ',<,:6trimethylcyclohe,anone does not. /ii0 There are two @H ' groups in semicarba&ide, however only one is involved in the formation of semicarba&one. Auring preparation of ammonia derivatives from aldehydes and etones, pH of the reaction mi,ture should be carefully controlled. G,plain. 3rite short notes on /i0 Rosenmund reduction /ii0 Crossed aldol condensation /iii0 Crossed Canni&aro reaction

4.

:. 9.

;. K.

3hat happens when propanone is treated with methyl magnesium bromide and the product obtained is hydrolysed> Nive one chemical test to distinguish between /i0 Acetophenone and ben&ophenone /ii0 =ropanal and diethyl ether

().

Nive the structure of the compound in each case with the formula C < H;O that satisfies the given criteria. /a0 #t gives a positive ',<6A@= test but negative haloform test. /b0 #t gives positive haloform test as well as a ',<6A@= test.

ALDEHYDES & KETONES

95

EXERCISE II
AIP25CAIEEE1SI*GBE C)&ICE C&RREC5

(. #dentify final product Q1L /a0 CH#7 '. 7. /b0 HC CH /c0 /d0 H'C R CH'

3hich one of the following reagent is used to convert acetone into ',76dimethylbutane6',76diol> /a0 2g Hg ! H 'O /b0 1n Hg ! HCl /c0 @a Hg ! @aOH /d0 All of these #dentify the product /H0 in the following reaction.

O ' @

CHO +

CH CH COO@a ( H) ( CH7CH 'CO ) ' O ( Heat )

7 '

/a0

CH = CH COOH CH 7 CH = C COOH 8

/b0 O ' @

CH = CH COOH

/c0

/d0 O ' @

<.

8 @O ' 3hat will be the product /=0 formed in the reaction given below> H+ CH7 CHO + @H ' OH ( =)
/a0 CH7 CH = @ OH /c0 Only anti aldo,ime

CH = C COOH 8 CH 7

/b0 Only syn aldo,ime /d0 @o product will be formed

4.

Consider the following se-uence of reaction.

The product " is. /a0 /b0 /c0 /d0

ALDEHYDES & KETONES

@a"H < ! H ' O ( A)

96

:.

H ' O ==

== O

( ) ' : ( ") ( ii ) H O ! OH
i " H
' '

The compounds /A0 and /"0 respectively are /a0 CH ' == /b0 CH 7 /c0 CH ' == /d0 CH 7 9.

OH and HOCH ' == O and HOCH ' and HOCH ' OH and CH 7 HO

== O == O == O == O

The order of reactivity of the following compounds with C: H 4 2g"r is /#0 C: H 4COC: H 4 /a0 ( # ) > ( ## ) > ( ### ) /##0 CH7CHO /b0 /###0 CH7COCH 7 /c0

( ### ) > ( # ) > ( ## )

( ## ) > ( # ) > ( ### )

/d0

( ## ) > ( ### ) > ( # )

;.

#dentify the product /H0 in the following reaction O O 88 88 Conc. @aOH =h C C H ( H) /a0 =hCOCO ' H /c0 =h CH ( OH ) CH 'OH /d0 =h CH = CH ' Among the following compounds, which will react with acetone to give a product containing /b0 =hCH ( OH ) CO ' @a

K.

C = @>
O 88 && && /a0 H ' @ C @H '

&& /b0 p @O ' C: H4 @H ' && && /d0 C: H 4 @H@H '

O 88 && /c0 H C @H '

(). #n the Canni&&aro reaction given below, OH '=h CHO =h CH ' OH + =hCO ' the slowest step is

ALDEHYDES & KETONES /a0 the attac of OH at the carbonyl group /b0 the transfer of hydride ion to the carbonyl group /c0 the abstraction of proton from the carbo,ylic acid /d0 the deprotonation of =h CH 'OH

97

Hydrolysis of an ester gives acid /A0 and alcohol /"0. #f compound /"0 is C ' H4OH and molecular formula of ester is C < H;O ' , then ester will be /a0 2ethyl formate /b0 Gthyl formate /c0 2ethyl acetate /d0 Gthyl acetate ('. ?chiffLs reagent is prepared by discharging the pin colour of the dye /a0 methyl orange /b0 pararosaniline hydrochloride /c0 rosaniline hydrochloride /d0 phenolphthalein ((. (7.

C = O + H 'O

OH C OH
/d0 C: H 4CHO

The value of e-uilibrium constant will be highest for /a0 HCHO /b0 CH7 CHO /c0 CCl7 CHO (<. Consider the following reaction,

C: H 4 CH 7

C = O + ( H ) H'O

C: H 4 CH 7

C = @.@H '

the compound /H0 is /a0 @H ' OH /b0 C: H 4 @H ' /c0 @H ' @H ' /d0 CH7 @H ' (4. A new carbon6carbon bond formation is possible in /a0 Canni&&aro reaction /b0 "aeyer Silliger O,idation /c0 Clemmensen reduction /d0 Reimer6Tiemann reaction (:. 2ost acidic hydrogen is present in O 88 /a0 CH 7 C CH 7

O O 88 88 /c0 CH 7 C CH ' C OCH 7

(9. #n the given reaction, OH 8
@H ' OH Cu H ( A)
+

O O 88 88 /b0 CH 7 C CH ' C CH 7 O O 88 88 && CH /d0 CH 7 C CH ' C ? 7 &&

the compound /A0 will be /a0

== O @H

/b0

== O @H

/c0

== O @H

/d0 none

ALDEHYDES & KETONES (;. #n the reaction, ( i ) "' H : K ' Cr' O9 ! H '?O < ' butene ( A ) ( ") ( ii ) H O ! OH
' '

98

the compound /"0 is /a0 butane /b0 (6butane dilute @aOH ( A) (K. C: H 4CH ' CHO The structure of compound /A0 would be /a0 C: H 4CH ' CH = CHCH 'C: H 4 /c0 C: H 4CH ' CH CH CHO 8 8 OH C: H 4 ').

/c0 butyraldehyde

/d0 butanone

C: H 4 8 C H CH CH = C CHO /b0 : 4 ' /d0 C: H4 CH ' CH CH ' CO ' H 8 OH

Compound /A0, CK H() O is inert to "r' in CCl < . Sigorous o,idation with hot al aline K2nO < yields ben&oic acid. /A0 gives yellow precipitate with ',<6dinitro phenyl hydra&ine as well as with @aO#. The possible structure of compound /A0 would be /a0 =hCOCH 'CH 7 /b0 =hCH ' COCH 7 /c0 =hCH ' CH 'CHO /d0 =hCH ( CH 7 ) CHO

Gther =hCOGt + 2g > The number of stereoisomers shown by the product of the following reaction would be /a0 ' /b0 7 /c0 < /d0 : ''. 3hich of the following dicarbo,ylic acid on heating with "aO gives cyclopentanone> /a0 ?uccinic acid /b0 Nlutaric acid /c0 Adipic acid /d0 =imelic acid @aH?O '7. 3hich of the following compound will undergo reaction with 7 at the slowest rate>

'(.

O 88 /a0 2e7C C CH 7
O 88 /c0 2e7C C C2e7

O 88 /b0 2e7C C C' H 4 O 88 /d0 2e7C C CH2e '

'<.

A substance C: H(' O does not react with 5ehlingLs solution but gives positive reactions for a carbonyl group. #t also gives positive iodoform reaction. 3hich of the following structure will best correspond to the above statements> /a0 CH7CH ' CH ( CH 7 ) COCH 7 /b0 CH 7CH 'COCH 'CH 'CH 7 /c0 CH7CH ' COCH ( CH7 ) '

/d0 CH 7CH 'CH 'CH 'CH 'CHO '4. A neutral compound /A0, molecular formula C < H;O ' reduce 5ehlingLs solution, liberates hydrogen when treated with sodium metal and gives a positive iodoform test. The structure of /A0 is /a0 CH7CH ( OH ) CH ' CHO /b0 CH 7CH 'CH 'CHO /c0 CH7COCH ' CHO /d0 CH 7COCH 'CH 'OH

ALDEHYDES & KETONES

99

EXERCISE III
AIP25CII51DEE SI*GBE C)&ICE C&RREC5 (.

O 88 CH 7 I C I H reacts most readily with.

/a0 H'@ I @H' /c0 =h I @H I@H' /b0 H ' @ I @H I C I @H ' 88 O /d0 H'@ I OH

'.

#dentify the product /P0 in the following se-uence of reactions.

@H ' OH ! H Conc. H '?O< C: H4 CO CH 7 ( H ) ( P)
+

/a0 =h C @H=h 88 O /c0 CH 7 C @HCH 7 88 O 7.

/b0 =h C @HCH 7 88 O /d0 C ' H4 C @HCH 7 88 O

Can you figure out /H0 in the following se-uence of reactions> ( H) ( i ) CiAlH < CH7CH ' CO CH ' COOC' H 4 CH 7CH 'COCH ' CH 'OH + C ' H 4OH ( A ) ( ii ) H O ! H +
'

/a0 CH ' O <.

/b0 CH ' OH CH 'OH ! OH

+ /c0 CH ' OH CH 'OH ! H /d0 HC@ 3hich is the product formed when '6methylcyclohe,anone is treated with selenium dio,ide in presence of acetic acid>

O 88
/a0

CHO
/b0

O 88

CH 7

O 88
/c0

CH 7
/d0

O 88

CH 7

4.

O 88 O Arrange the following compounds in the decreasing order of their acidic strength. CH CH CH 7 CHO CH 7 CO CH 7 CH 7 CO CH ' CO CH 7 ( #) ( ## ) ( ### ) ( #S )

ALDEHYDES & KETONES /a0 ( #S ) > ( ## ) > ( # ) > ( ### ) /c0 ( # ) > ( #S ) > ( ## ) > ( ### ) :. /b0 /d0

100

( #S ) > ( ## ) > ( ### ) > ( # ) ( ### ) > ( ## ) > ( #S ) > ( # )

#dentify the missing reactant in the following reaction from the given four options> ( i ) 1n C: H 4 CHO + ( R ) C: H 4 CH = CH COOC ' H 4 ( ii ) H' O ! @H <Cl
( iii )
Heat

/a0 CH7CH ' COOC' H 4 /c0 CH 7 CH COOC 'H 4 8 "r 9.

: 4 7 CH ' Cl CH 'Cl ( ii ) CH7 Ci ! Heat >

/b0 "r CH ' COOC ' H 4 /d0 HO CH ' COOC' H 4

( i) ( C

( iii )

CHO CHO

The product of the reaction is /a0

CH = CH CH ' 8 CH ' Cl CHO CH ' CH ' CH '

CH
/b0

CH 8 CH CH CH CH CH '

/c0 ;.

/d0

#dentify the ma$or product formed in the following reaction. dil. @aOH CH7 CO ( CH ' ) 7 CHO 2a$or product. Heat O 88 CHO /a0 /b0 /c0 CHO 3hat will be the product /H0 in the following reaction>
( ) ' < CH7CH ' CHO ( H) . ( ii ) CiAlH <
i KC@ ! H ?O

O 88 CHO
/d0

K.

().

OH OH 8 8 /a0 CH7CH ' CH CH ' OH /b0 CH7CH ' CH CH ' @H ' /c0 CH7CH ' CH ' CH 7 /d0 CH 7CH 'CH 'CH ' @H ' #dentify the ma$or product formed in the following reaction.

OH OH 8 8 CH CH 8 8
dil. H '?O < ma$or product.

ALDEHYDES & KETONES

101

CH = = CH 8 8
/a0 /b0

O CH ' C 8 8

OH CH ' CH 8 8
/c0 /d0

C C 8 8

O 88
((.

88 O
/a0 ('.

C' H4O@a 1n ! Hg ( A ) ( ") . Heat conc. HCl

The product /"0 formed in the above reaction is

O 88
/b0 /c0 /d0 @one of these

3hat will be the ma$or product /H0 formed in the following reaction> Cl O 8 88 C ' H4O@a C: H 4 CH C CH 7 ( H) in C ' H 4OH O 88 C H CH C CH 7 /a0 : 4 8 OC' H 4 /b0 C: H 4CH ' CH 'COOC ' H4 O 88 C

(7.

/c0 C: H 4 CH COOC ' H 4 /d0 C: H 4 CH CH ' 8 CH 7 3hat will be the product /10 formed in the following reaction>

O
( ) ( ii ) HCl ( 1 )
i @aOH

O COOH
/a0 /b0

COOH OH

/c0

COOH OH

/d0

COOH 8 OH

OH

ALDEHYDES & KETONES (<.

102

(4.

Aldol condensation, between which of the following compounds followed by dehydration gives methyl vinyl etone> /a0 5ormaldehyde and acetone /b0 5ormaldehyde and acetaldehyde /c0 Two molecules of acetaldehyde /d0 Two molecules of acetone An organic compound on treatment with H#O < gives cyclopentanone and formaldehyde. The compound is OH O 8 88 CH CH ' OH CH ' OH /a0 /b0

/c0 (:.

OH CH ' OH

/d0

CH ' OH

Consider the following reaction,

dil. @aOH CHO + CH 7CHO ( H)

3hich of the following statement is not correct> /a0 #t is a crossed aldol condensation reaction /b0 The reaction yields one more condensation product besides /H0 /c0 Compound /H0 is

CH ' CH 'CHO

(9.

/d0 Compound /H0 is commonly nown as cinnamaldehyde Arrange the following compounds in decreasing K e- Ls for cyanohydrin formation. p @O ' C: H < CHO, ( #) /a0 ( #S ) > ( ### ) > ( # ) > ( ## ) /c0 ( #S ) > ( # ) > ( ### ) > ( ## ) O CH 72g"r ( e,cess ) == O ( H ) . 3hat is /H0> H 7O + /a0 =h CO =h, ( ## ) C :H 4CHO, ( ### ) /b0 /d0 CH 7CHO ( #S )

( ### ) > ( # ) > ( ## ) > ( #S ) ( ## ) > ( # ) > ( ### ) > ( #S )

(;.

CH 7 CH 7 O

OH OH CH 7

OH

/b0

HO CH 7 O OH

/c0 (K.

/d0

The final product of the following se-uence of reaction is H 'C =O H 7O + 2g > ( CH7O ) ' CHCH 'CH 'CH ' "r heat

ALDEHYDES & KETONES O 88 /a0 CH 7O C CH 'CH 'CH 'CH 'OH O 88 /c0 H C CH 'CH 'CH 'CH 'OH '). O 88 /b0 CH 7 C CH 'CH 'CH ' CH 'OH O O 88 88 /d0 H C CH 'CH 'CH ' C H

103

'(.

Compound QAL /molecular formula C7 H; O 0 is treated with acidified potassium dichromate to form a product Q"L /molecular formula C7H : O 0. Q"L forms a shining silver mirror on warming with ammoniacal silver nitrate. Q"L when treated with an a-ueous solution of H ' @CO@H@H ' .HCl and sodium acetate gives a product QCL. #dentify the structure of QCL. /a0 CH7CH ' CH = @@HCO@H ' /b0 CH 7 C = @@HCO@H ' 8 CH 7 /c0 CH 7 C = @CO@H@H ' /d0 CH 7CH 'CH = @CO@H@H ' 8 CH 7 3hen a mi,ture of CH 7CH 'CH 'Cl and CH7COCH ' Cl is treated with K# in acetone, then /a0 the products are CH 7CH 'CH ' # and CH7C ( # ) CH ' Cl 8 OK /b0 CH7COCH ' Cl reacts faster than CH 7CH 'CH 'Cl /both by ?@ ' reaction0 /c0 CH7CH ' CH ' Cl reacts faster than CH7COCH ' Cl /both by ?@ ' reaction0 /d0 both under goes reaction at the same rate as both are (* halides. 3hich of the following compound undergoes ready decarbo,ylation on warming> /a0 =hCOCO ' H /b0 =hCOCH 'CH 'CO ' H /c0 =hCH ( OH ) CH 'CO ' H /d0 HO ' CCH ' CO ' H =hCOCO ' H > + CO
Conc. H '?O <

''.

'7.

'<.

The missing product of the following reaction is /a0 =hCO=h /b0 =hCOCH 7 /c0 =hCO ' H /d0 =hCOCO=h #n the reaction, O,idising CH7 CH = CH CHO CH7 CH = CH COOH, the o,idi&ing agent can be agent /a0 Al aline K2nO < /c0 "enedictLs solution /b0 Acidified K ' Cr' O9 /d0 All of the above

'4.

Consider the following carbonyl compounds

3hich of the following is correct decreasing order of their dipole moment> /a0 = J R J T J ? /b0 ? J R J T J = /c0 ? J T J R J = /d0 T J ? J R J =

ALDEHYDES & KETONES

104

EXERCISE IV
2&RE 5)A* &*E C)&ICE C&RREC5 (. Acetone can be prepared in the laboratory by /a0 the treatment of propyne with a-ueous H '?O < in the presence of Hg?O < /b0 the dehydrogenation of isopropyl alcohol at 7))*C in the presence of Cu. /c0 the o,idation of isopropyl alcohol with chromic acid /d0 the reaction of ethyl acetate CH7 C OGt with methyl magnesium iodide /e,cess0. 88 O 3hich of the following pairs on reaction in dry ether and subse-uent hydrolysis will yield '6 methyl6'6butanol> /a0 CH7COOC' H 4 and CH7 2g# /c0 CH7CH ' COOC' H 4 and CH7 2g# /e,cess0 7. <. /a0 TollenLs test /b0 5ehlingLs test /b0 CH7COOCH 7 and C' H 4 2g# /d0 CH7CH ' COCH 7 and CH 72g# /c0 #odoform test /d0 A@= test

'.

Acetophenone and =henyl acetaldehyde can be distinguished by #n the given reaction, O 88 (. "r' ! H + H 7O + CH 7CH ' C CH 'CH 7 [ H ] [ P] '. OH ! H O
'

the products are

O 88 /a0 [ H ] . CH 7 CH ( "r ) C CH 'CH 7

/c0 [ P ] . CH 7 CH CH 'CH 7 8 COOH 4. #ntramolecular Canni&&aro reaction is given by /a0 C: H 4COCHO

/b0 CH 7 CH CH ' CH 7 8 COO /d0 [ P ] . CH 7CH 'CH 'CH 'COOH

/b0 CHO CHO /d0 C: H 4CH ' CO CH 7

CHO
/c0

CHO
:. Acetaldehyde when heated in presence of concentrated H '?O < will give

OH 8 /a0 CH 7 CH CH 'CHO

/b0 CH7 CH = CH CHO

ALDEHYDES & KETONES

105

H 7C
/c0

O C 8 O C C 8 O

H CH 7
/d0 @o reaction ta es place

9.

CH 7 H The Canni&&aro reaction is given by

/a0 trimethyl acetaldehyde /c0 ben&aldehyde /b0 acetaldehyde /d0 trichloroacetaldehyde

;.

Choose the correct statements. /a0 Acetaldehyde on polymeri&ation gives paraldehyde /b0 5ormaldehyde gas on polymeri&ation gives metaformaldehyde /c0 Acetaldehyde forms ?chiffLs base with formaldehyde /d0 "en&aldehyde does not polymeri&e

K.

3hich of the following is a method to prepare cyclopentanone>

OH 8
/a0
K ' Cr'O 9 , H
+

"aO, /b0 HO ' CCH ' CH 'CH 'CH 'CO ' H

O 88 =d ! "a?O < /c0 CH 7CH ' CH 'CH ' C Cl Tuinoline + ?

CO ' H 8
/d0 ().
CiAlH <

3hich of the following compound is capable of showing aldol condensation> /a0 CH7CH ' CH ' CHO /c0 CH 7 CH CH 'CHO 8 CH7 /b0 CH 7 CH CHO 8 CH 7 /d0 =h CO CH2e '

((.

=h H 7C

H ' @ OH H '?O< H7 O C = O ( A ) ( " ) =roducts.

+

ALDEHYDES & KETONES The final products of the reaction could be /a0 =hCO ' H and CH 7 @H ' /c0 CH7CO ' H and CH 7 @H ' ('. CH 7COCHO can be obtained by the o,idation of /a0 CH7CH ' CHO by ?eO'
+ /c0 CH7CH ' CH ' OH by K2nO < , H

106

/b0 =h @H ' and =hCO ' H /d0 CH7CO ' H and =h@H ' /b0 CH7COCH 7 by ?eO'
+ /d0 CH 7 CH CHO by K ' Cr' O9 , H 8 OH

COCH 7 8
(7. The compounds and

CHO 8

can be distinguished by

8 CO ' H

8 CO ' CH7
/b0 @H < OH and Ag@O7 /d0 @aOH and Cu?O <

/a0 ', <6dinitrophenyl hydra&ine /c0 @aHCO7 solution (<. =h CH ' C CH ' Cl on reduction gives 88 O /a0 =hCH ' CH CH 7 by CiAlH < 8 OH /c0 =hCH ' CH CH 7 by H ' ! @i 8 OH (4. CH7COCH ' CH 7 on aldol condensation gives

/b0 =h CH'CH'CH 'Cl by 1n Hg!conc. HCl

/d0 =hCH ' CH 'CH 'OH by @ ' H < , OH

CH 7 8 /a0 CH 7CH ' C = CH C CH 'CH 7 ( in presence of dil. @aOH ) 88 O CH7 8 /b0 CH 7CH ' C = C C CH 7 ( in presence of dil. @aOH ) 8 88 H 7C O

CH 7 8 /c0 CH 7CH ' C = CH C CH 'CH 7 ( in presence of dil. H '?O < ) 88 O CH 7 8 /d0 CH 7CH ' C = C C CH 7 ( in presence of dil. H '?O < ) 8 88 H 7C O

ALDEHYDES & KETONES

107

EXERCISE V
2A5C) 5)E F&BB&EI*G *ote : Gach statement in column # has one or more than one match in column ##. (.

Column - I $Reactions%
I. II. CH 7CH = CHCHO CH 7CH = CHCOOH CH 7CH = CHCHO CH 7CH 'CH 'CH 'OH A. 8. C. !.

Column - II $Rea ents%

CiAlH < @a"H < Ammoniacal Ag@O7 H ' % =d ! "a?O <

R CH 'OH III. R COOH CH 7CH 'CHO I4. CH 7CH 'COCl

'.

Column - I
I. II. C: H 4CHO CH 7C CH A. 8. C. !.

Column - II
gives precipitate with ', <+dinitrophenylhydra&ine gives precipitate with Ag@O7 is a nucleophile is involved in cyanohydria formation

III. C@ I4. #

*ote : Gach statement in column # has only one match in column ##. 7.

Column - I $Reactions%
I. II. Canni&&aro reaction ?tephenLs reaction A. 8. C. !. E.

Column - II $Rea ents%

@aOGt in GtOH @aOH =d ! "a?O < /"oiling ,ylene0 1n ! Hg conc. HCl ?nCl' ! HCl

III. Clemmensen reduction I4. RosenmundLs method

ALDEHYDES & KETONES

108

ASSER5I&* A*! REAS&* 5FPE !irections : Read the follo3in Guestions and choose : $A% #f both Assertion and Reason are true and Reason is the correct e,planation of the Assertion. $8% #f both Assertion and Reason are true but Reason is not correct e,planation of the Assertion. $C% #f Assertion is true but Reason is false. $!% #f Assertion is false but Reason is true. :. Assertion : Chloral hydrate is a stable compound although it is a gemdiol. Reason : #t is due to its high molecular weight. /a0 A (. /b0 " /c0 C /d0 A Assertion : 5ehlingLs solution test is given by all aliphatic aldehydes. Reason : Aliphatic aldehydes can be easily o,idi&ed even with mild o,idi&ing agents. /a0 A 7. /b0 " /c0 C /d0 A
+ Assertion : =rimary alcohols can be easily o,idi&ed to aldehydes using K ' Cr' O9 ! H .

Reason : Aldehydes are susceptible to further o,idation to give carbo,ylic acids. /a0 A ;. /b0 " /c0 C /d0 A Assertion : '6methyl propanal undergoes Canni&&aroLs reaction. Reason : #t has an hydrogen atom. /a0 A <. /b0 " /c0 C /d0 A Assertion : :6o,oheptanal on treatment with dilute @aOH gives (6acetyl cyclopentene. Reason : #n intramolecular aldol condensation, the carbanion should be formed from carbon of etone and it attac s on aldehydic carbon to form finally , unsaturated carbonyl compound. /a0 A /b0 " /c0 C /d0 A

ALDEHYDES & KETONES

109

PASSAGE 8ASE! PR&8BE2S Aldehydes and they have a polar etones are especially susceptible to nucleophilic addition reaction because

C = O group. The polarity of

C = O group arises due to electronegativity difference

between carbon and o,ygen.

C=O
by acid.

=ositive charge on carbon ma es it reactive towards the nucleophile. This addition is catalysed Reactivity of carbonyl compound towards nucleophilic addition increases with increase in the electron deficiency at carbonyl carbon. Thus, ( # ) groups increase while ( + # ) groups decrease the reactivity of carbonyl compounds. (. '. 7. 3hich among the following is most reactive towards nucleophilic addition reaction> /a0 5CH ' CHO /b0 ClCH ' CHO /c0 "rCH ' CHO /d0 #CH ' CHO Carbonyl compounds show nucleophilic addition reaction with /a0 HC@ /b0 @aH?O7 /c0 CH7 2gCl /d0 All of these 3hich among the following isomeric compounds is most reactive towards nucleophilic attac >
O 88 /a0 CH7CH ' CH 'CH ' C H O 88 /c0 CH 7CH ' C CH 'CH 7

O 88 /b0 CH7CH ' CH ' C CH 7 /d0 All are e-ually reactive

<.

3hich of the following compound undergoes hydration most readily> /a0 CH7COCH 7 /b0 CH7CH ' CHO /c0 CH 7CHO 3hich of the following reaction does not involve nucleophilic attac on the /a0 Canni&&aro reaction /c0 RosenmundLs reduction

/d0 HCHO

4.

C = O group>

/b0 Aldol addition /d0 Reduction by CiAlH <

ALDEHYDES & KETONES

110

A*SEERS EXERCISE I
C8SE PR&8BE2S (. /i0 "en&ene6(, <6dicarbaldehyde or p6aldoben&aldehyde /ii0 "ut6'6en6(6al or, '6"utenal /iii0 =entane6', <6dione

'.

'6Gthylben&aldehyde

CHO 8 C' H4

7.

/i0 "y using 1n Hg ! conc. HCl% ClemmensenLs reduction

/ii0 "y using @H ' @H ' ! OH % 3olf6Kishner reduction

<.

4.

The compound would be CH 7CH CHO or CH 7COCH 7 . =ropanal can be distinguished from propanone in the respect that former gives TollenLs test while later does not. These do not give Canni&&aro reaction as they have hydrogens. /i0 #n ', <, : 6 trimethylcyclohe,anone due to the presence of three methyl groups at position /w.r.t the

C = O 0% the nucleophilic attac by the C@ ion does not occur due to steric

hindrance. ?ince there is no such steric hindrance in cyclohe,anone, therefore, nucleophilic attac by the C@ ion occurs readily and hence cyclohe,anone cyanohydrin is obtained in good yield.

&& @H && C @H && /ii0 #n semicarba&ide, @H the lone pair of electrons on nitrogen ' and 7 are involved ' ' /(0 /'0 88 /70 O in resonance with C = O group, so can not function as nucleophile which the lone pair of
electron on nitrogen ( is not delocali&ed, so can undergo nucleophilic attac . OH 8 ( i ) CH72g"r CH 7COCH 7 CH C CH 7 D 7 ( ii ) H ! H 'O 8 CH 7

;.

ALDEHYDES & KETONES K.

111

/i0 Acetophenone ( =hCOCH 7 ) will give positive iodoform test while ben&ophenone ( =hCO=h ) will not give. /ii0 =ropanal gives positive TollenLs or 5ehlingLs test while diethyl ether does not give this test. /a0 CH7CH ' CH ' CHO /b0 CH7COCH ' CH 7

().

ALDEHYDES & KETONES

112

EXERCISE II
AIP25CAIEEE1SI*GBE C)&ICE C&RREC5 (. /b0 :. /a0 ((. /d0 (:. /b0 '(. /b0 '. /a0 9. /d0 ('. /c0 (9. /c0 ''. /c0 7. /d0 ;. /b0 (7. /c0 (;. /d0 '7. /c0 <. /a0 K. /d0 (<. /c0 (K. /b0 '<. /a0 4. /b0 (). /b0 (4. /d0 '). /b0 '4. /a0

EXERCISE III
AIP25CII51DEE SI*GBE C)&ICE C&RREC5 (. /a0 :. /b0 ((. /c0 (:. /c0 '(. /b0 '. /b0 9. /b0 ('. /b0 (9. /c0 ''. /d0 7. /c0 ;. /d0 (7. /c0 (;. /a0 '7. /c0 <. /b0 K. /b0 (<. /a0 (K. /c0 '<. /c0 4. /b0 (). /b0 (4. /c0 '). /a0 '4. /c0

EXERCISE IV
2&RE 5)A* &*E C)&ICE C&RREC5 (. :. /a, b, c0 /b, c0 '. 9. /c, d0 /a, c0 7. ;. /a, b, c0 /a, b, d0 <. K. /b, c0 /a, b0 4. /a, b, c0

(). /a, c0 (4. /a, d0

((. /a, d0

('. /a, b0

(7. /b, c, d0

(<. /a, b, d0

ALDEHYDES & KETONES

113

EXERCISE V
2A5C) 5)E F&BB&EI*G (. '. 7. # ( C ) % ## ( " ) % ### ( A ) % #S ( A ) # ( " ) % ## ( G ) % ### ( A ) % #S ( C )

# ( A ) , ( C ) , ( A ) % ## ( " ) , ( C ) % ### ( " ) , ( C ) , ( A ) % #S ( " ) , ( C )

ASSER5I&* A*! REAS&* 5FPE (. /c0 '. /a0 7. /d0 <. /b0 4. /a0

PASSAGE 8ASE! PR&8BE2S (. /a0 '. /d0 7. /a0 <. /d0 4. /c0