INTRODUCTION

Both aldehydes & ketones contain carbonyl group as their functional group. Structure of carbonyl group Both aldehydes & ketones have carbonyl group as the functional group. The carbonyl carbon is sp2 hybridised & it uses sp2 hybrid orbitals to form 3 bonds, one with oxygen atom & remaining 2 with two other atoms or groups (R or H). All these 3 bonds lie in same plane at the angle of 120. The unhybridized p orbital of carbonyl carbon form - bond with oxygen atom by sidewise overlapping with half filled p orbital of oxygen atom. Since carbon & oxygen have different values of electronegativity, the bond between carbon & oxygen is polar. Infact electron density around the oxygen atom is increased which causes the development of partial positive charge ( +) on carbon & partial negative charge () on oxygen. Thus the carbonyl carbon is an electrophilic & carbonyl oxygen is nucleophilic centre. Illustration 1. Give the IUPAC name for (i) CH3CHO (ii)

bond O

bond

Orbital picture of carbonyl group

CH

CHO

Solution:

(i) Ethanal (ii) 2, 2 diphenyl ethanal

Illustration 2. Write structure of the following compounds: (i) 3-phenyl 2-propenal (ii) 1, 5 pentanedial Solution: (i)
CH CH CHO

(ii)

OHC CH2 CH2 CH2 CHO

Exercise 1. Write the formula of the following compound: Cyclopentane carbaldehyde Exercise 2. Calculate the number of sigma bonds in diphenyl ketone. GENERAL METHODS OF PREPARATION OF ALIPHATIC ALDEHYDES & KETONES

1. From Alcohols (a) By Direct oxidation: Aldehydes are prepared by oxidation of 1 alcohols. Refer to Alcohols (b) By catalytic dehydrogenation When vapours of 1 or 2 alcohols are passed over copper gauze, they get dehydrogenated to form aldehydes or ketones. Cu / 573K CH3 CH2CH2OH CH3CH2CHO+ H 2
n propyl alcohol Pr opionaldehyde

Dehydrogenation reaction is a better method of preparation because there is no risk of further oxidation of aldehyde. (c) By using PCC PCC stands for pyridinium chlorochromate. It is an equimolar mixture of CrO3, HCl and pyridine. It is used to oxidise 1 alcohol to aldehyde and 2 alcohol to ketones without affecting double or triple bond. Illustration 3. Complete the following reaction by writing down the major product: OH (i)
PCC CH2Cl2

(ii ) Solution: (i)

OH

PCC OH CH2Cl2

O

PCC CH 2Cl2

(ii)

PCC OH CH Cl
2 2

O
H

Exercise 3. Why is it important to distil out the aldehyde as soon as it is formed by the oxidation of primary alcohol? 2. From Acid chlorides Aldehydes are prepared from acid chlorides by reaction with H2 in the presence of palladium catalyst supported on BaSO4.
O R C Cl
H2
Pd, BaSO 4 ,S Boiling xylene

O R C H HCl (Rosenmunds reduction)

Ketones are obtained by reacting acid chlorides with dialkyl cadmium. 2RCOCl + CdR '2 2RCOR'+ CdCl2 Illustration 4. Prepare ethanal by reduction method.

Solution:
H3C

O C
Pd / BaSO4 H3C Cl H2 xylene

O C Ethanal H HCl

Exercise 4. Write the structures of compound A and B in the following reaction: O

PCC HOH2C B CH2 Cl

CH2 CH2 C

2 A Cl BaSO4

H / Pd

3. From fatty acids (a) By heating calcium salt of fatty acid Aldehydes are obtained by heating calcium salt of fatty acids with calcium formate.
CH3COO Ca CH3COO Calcium acetate OOCH Ca OOCH Calcium formate 2CH3CHO 2CaCO3 Acetaldehyde

Ketones are formed by distilling calcium salt of fatty acids alone.

CH3COO Ca 675K CH3COO H3C O C CH3 CaCO3

Similarly mixed ketones, can also be obtained by similar reactions:

CH3COO Ca Ca CH3COO OOCC2H5 OOCC2H5 O

2CH3 CC2H5 2CaCO3

(b) By passing vapours of fatty acids over manganese oxide In this method, formic acid alone gives formaldehyde. Acetic acid gives acetone & the mixture of two acids gives acetaldehyde. MnO 2HCOOH HCHO + H2O + CO2 575K O 2CH3 COOH CH3 C CH3 + H2O + CO 2
MnO 575K MnO CH3 COOH + HCOOH CH3CHO + H 2O + CO 2 575K ||

4. From Alkynes: (Refer to hydrocarbons) 5. By reductive ozonolysis of alkenes: (Refer to hydrocarbons)

Illustration 5. What happens when (give equation only)?

(i) Ethyne is treated with dilute H2SO4 in the presence of HgSO4. (ii) propan-2-ol is treated with Cu at 573 K. Solution: (i) (ii)
H3C CH OH
Br2 ( ) 3 CH3 CH2 CH 3 A B h Alc. KOH ( ii ) H2 O / Zn C i O dil. H2 SO 4 CH CH CH3 CHO HgSO4

O
H3C CH3 573K
Cu

CH3

Illustration 6.

( mixture )

Identify A, B and C. Solution:

Br2 H3C h

CH3CH2CH3

CH Br

CH3

(A)

Alc. KOH

( i) O 3 CH3CHO HCHO H3C ( ii ) H2O / Zn (C)

Exercise 5. Convert 2 chloro but-2-ene to 2-butanone.

CH (B)

CH2

Exercise 6.

O3 LiAlH4 ( B ) ( C3 H6O ) ( C ) ( C 3H 8O ) Hydrocarbon A ( C6 H12 ) Zn H2 O

The compound (C) gives yellow precipitate with I 2 and NaOH. What is the structure of compound A?

Exercise 7. (i) What is the hybrid state of carbon 1 & 2 in ethanal? (ii) What product is obtained in the following reaction?

Zn. dust O 3 H2 O

Exercise 8. OsO4 (A) H + (B) (major). (B) is

(A)
O

(B)

CHO

(C)

OH

(D)

PREPARATION OF AROMATIC ALDEHYDES & KETONES 1. By oxidation of alkyl benzene Aromatic aldehydes are obtained by oxidation of side chain in the aromatic ring.
CH3 HC OCOCH3 OCOCH3
3[ ] ( CH3 CO) O

CHO

CrO O

H2 O

2CH3COOH Benzaldehyde

CrO2Cl2 (Etard reaction)

Illustration 7. How will you prepare benzaldehyde commercially? Solution: It is prepared form toluene.
CH3
Cl 2 / h heat

CHCl2
H 2O 1000 C

CHO

2. By Friedel crafts reaction (Refer to hydrocarbons) Illustration 8. In the following electrophilic substitution reaction. COCH3

AlCl 3 + ( CH3CO ) 2 O

(i) Identify the compound A. (ii) Write the structure of the electrophite.

Solution:

(i)
A H3C

O C OH

(ii) Electrophile is H3C Illustration 9. Complete the following

O CH3CH2 CCl
AlCl3

O C

Zn / Hg B A HCl

Solution:
A=

O C CH2 CH3 B=

Exercise 9.
COCl

AlCl3 X , X is

N2O

(A) O2N

CO

(B )

N2 O

(C)

COCH3

(D )

O C

Exercise 10.
Cl H O O H Cl
AlCl 3 A; Identify the A. heat

(A)

H O H Cl

(B )

(C)

(D )
O

OH

O Cl

3. By Gattermann Koch Reaction In this method aromatic aldehydes are prepared by formylation of aromatic ring with carbon monoxide.
CHO

3 CO HCl

AlCl

benzaldehyde

4. From Grignards reaction Both aliphatic & aromatic aldehyde can be obtained by this method. HCN on treatment with Grignards reagent & subsequently followed by hydrolysis yield an aldehyde.
OH HCN CH3MgBr
Dry H3CHC Ether

NMgBr

+ H2 O CH3CHO

Mg Br

NH3

Similarly
CH3 C N C NMgI CH3 C O OH

CH3 MgI

H2O

NH3 Mg I

PHYSICAL PROPERTIES OF ALDEHYDES & KETONES (i) Physical state Most of aldehydes (except formaldehyde which is a gas) are liquids at room temperature. The lower ketones are colourless liquids and have pleasant smell. (ii) Boiling points Aldehydes & ketones have relatively high boiling points as compared to hydrocarbons of comparable molecular masses due to polar carbonyl group, which bring stronger intermolecular dipole dipole interactions between the opposite ends of C = O dipoles. Ketones are relatively more polar than their corresponding isomeric aldehydes due to the presence of two electron repelling alkyl group around the carbonyl carbon. (iii) Solubility The lower members of aldehydes & ketones (upto four carbon atoms) are soluble in water. It is due to their capability of forming hydrogen bonds with water molecules. The solubility of these compounds in water decreases with the increase in the size of alkyl group because of the increase in magnitude of non polar part in the molecule.

R C R O H

O H O C

CHEMICAL PROPERTIES Aldehydes & ketones are highly reactive compounds, they undergo nucleophilic addition reactions. Their reactivity is due to presence of a polar carbonyl group. The positively charged carbon atom of carbonyl group is readily attacked by nucleophilic species for initiation of the reaction. This leads to formation of intermediate anion which further undergoes the attack of H+ ion or other positively charged species to form the final product. The reaction in general may be represented as:
Nu Nu
+

Nu

slow step1

fast C O step2 C

Planar

OH

Relative reactivity of aldehydes & ketones In general ketones are less reactive than aldehydes on a account of following facts: (i) Electron releasing effect of two alkyl groups, decreases the magnitude of positive charge on ketones. (ii) Steric effect caused by two alkyl groups also hinders the approach of the nucleophile to the carbonyl carbon.
H C H O > H R C O > R R C O

Reactivity decreases

Illustration 10. Draw (i) resonance structures and (ii) an atomic orbital representation of the H
C H O

Solution:

(i)
H

O C

(ii)
H H C

Illustration 11. Ethanal is more soluble in water than ethyl chloride. Explain. Solution: This is due to the ability of ethanal to form hydrogen bonds with water.

Exercise 11. Predict the value of the angle (a) and (b) in the following figure.

H a b C O H

Exercise 12. Explain the following fact: Dipole moment of ethanal = 2.72 D Dipole moment of diethyl ether = 1.18 D

Exercise 13. Give the increasing order of boiling point among following compounds. I : CH3CH2CH2OH II : CH3CH2OCH3 III : CH3CH2CHO IV : CH3CH2CH3

TYPE OF CHEMICAL REACTIONS IN CARBONYL COMPOUNDS (i) Addition across C = O bond. (ii) Replacement of carbonyl oxygen by other groups. (iii) Oxidation (iv) Reduction (v) Reaction with alkalies (vi) Miscellaneous reactions

1. Addition across C = O bond Sr. Addition of No. 1. Hydrogen cyanide Substrate Product

C OH

CN (Cyanohydrin)

2.

Sodium bisulphite (NaHSO3)

C OH

SO 3 Na (Bisulphite addition product)

HCHO Grignard reagent (RMgX) followed by hydrolysis Aldehydes (except formaldehyde) Ketones 4. Alcohols (ROH)

H3 C CH2 OH 10 alcohol 2 alcohol

3.

3 alcohol

Hemiacetal which finally converts to acetal

Illustration 12. Write the structure of compound A and B

H O HCN A B ( CH3 ) 2 C = O
3 +

Solution:
A H3C

OH C CH3 CN B H3C

OH C CH3 COOH

Exercise 14. Give the product of the reaction of acetaldehyde with sodium hydrogen sulphite.

Exercise 15. The most reactive compound towards formation of cyanohydrin on treatment with KCN followed by acidification is (A) Benzaldehyde (B) p Nitrobenzeldehyde (C) Phenyl acetaldehyde (D) p Hydroxybenzeldehyde

2. Replacement of carbonyl oxygen atom with other groups

10

(a) Reaction with ammonia derivatives Aldehydes & ketones react with a number of NH 3 derivatives such as hydroxyl amine, hydrazine, semicarbazide etc, in weak acidic medium. In general, if we represent these derivatives by NH2 G, then their reaction with aldehydes & ketones can be represented as follows:
C O H2N G H C N G H2 O

Ammonia derivatives & their products with carbonyl compounds G OH Ammonia Derivative NH2OH Hydroxylamine Product obtained

NOH

Oxime NH2 NH2NH2 Hydrazine

C NNH2

Hydrazone NHC6H5 NH2NHC6H5 Phenyl hydrazine

NNHC6H5

Phenyl Hydrazone
NH NO2
H2NHN NO2
C N NH NO2

O2N

O2N

2, 4 dinitrophenyl hydrazine NHCONH2

2, 4 dinitrophenyl hydrazone
O NNH CNH2 Semicarbazone

O 2N

O H2NHN CNH2 Semicarbazide

(b) Reaction with ammonia

Like ammonia derivatives, ammonia also reacts with aldehyde (except formaldehyde) & ketones to form the products, called imines.
H3C C H O NH3 H H3C C NH2 OH -H2O H3C C NH

H Acetaldimine

However, formaldehyde reacts with NH3 to form hexamethylene tetramine, (CH2)6N4 also known as urotropine as shown below:
N H 2C CH2 N CH2 Hexamethylene tetramine CH2 N CH2 N CH2

6CH2O

4NH3

-6H2 O

Acetone reacts with NH3 to form diacetonamine

H3C 2CH3COCH3 NH3 H3C CH2COCH3 NH2 H 2O

4 - amino - 4 - methyl pentan - 2 - one

(c) Reaction with primary amines Aldehydes & ketones react with 10 amines to form Schiff;s bases. These compounds are also called imines. RCHO+ H2NR RCH = N R+ H2O
Aldehyde Amine Aldimine A Schiff ' s base

R C R O H2NR

R C R N Ketimine R H 2O

Ketone

(d) Reaction with PCl5 or SOCl2 (thionyl chloride) Aldehydes or ketones with PCl5 or thionyl chloride to form geminal dihalides.
Cl C O PCl 5 C Cl Cl
C O Pyridine SOCl2 C Cl SO 2

POCl 3

Illustration 13. Write the structural formula of the following ammonia derivatives:

12

Solution:

(i) 2, 4 dinitrophenyl hydrazine (ii) Semicarbazide (iii) Hydroxyl amine NO2 (i)
O 2N NHNH2

(ii) H2NNHCONH2 (iii) H2NOH Exercise 16. Which NH2 group of semicarbazide H N CONH NH undergo condensation with the 2 2 carbonyl group?
( a) ( b)

Exercise 17. Complete the reaction: NH2 CONHNH2 (i) CH3CHO (ii)
NH NH ( CH3 ) 2 CO
2 2

Exercise 18.
O
NH2 CH2 CH 3 + A, where A is

(A)

(B )
N OH

CH2

(C)

(D )

CH2CH3

3. Oxidation Aldehydes are easily oxidised to carboxylic acids containing the same number of carbon atoms, as in parent aldehyde.
O R C H [O] R C OH O

The reason for this easy oxidation is the presence of a hydrogen atom on the carbonyl carbon, which can be converted into OH group without involving the cleavage of any other bond. Hence, aldehydes are oxidised not only by strong oxidizing agent but also by weak oxidizing agents. As a result, aldehydes act as strong reducing agents. Aldehydes reduce Tollens reagent to Ag & appear in the form of silver mirror. This test is called silver mirror test. It is given by all aldehydes & reducing sugars.
RCHO + 2 Ag ( NH3 ) 2 + 3OH RCOO + 2Ag + 4NH3 + 2H 2O ( Silver mirror ) +

Aldehydes (except benzaldehyde) reduce Fehlings solution (Cu+2 reduced to Cu+) which is an alkaline solution of cupric (Cu2+) ion complexed with tartarate ion. RCHO + 2Cu2 + + 3OH RCOO + 2Cu + + 2H2O
red ppt 2+

Aldehydes also reduce Benedicts solution (Cu complexed with citrate ion) to Cu+. Aldehydes & ketones with a methyl or methylene group adjacent to the carbonyl group are oxidised by SeO2
CHO CH3CHO SeO 2 CHO H2O Se

CH3 COCH3 + SeO 2 CH3COCHO + H 2O + Se

Ketones are also oxidised by caros acid (H2SO5) or peroxybenzoic acid (C6H5CO3H) to esters. H2 SO5 RCOR '+ O RCOOR '
O O

6 H5 CO 3 H C

O C6H5CCH 3
C6H5 CO3 H H 5C 6

O O C CH3

It is called Bayer villiger oxidation. It is exactly oxygen insertion between carbonyl carbon & the larger of two groups attached to it. Haloform Reaction
CH3CHO 3I2 NaOH I 3CCHO 3HI

Hydrolysis CHI3 HCOONa

iodoform (yellow ppt)

Due to the formation of yellow ppt. of iodoform in this reaction, it is known as iodoform test & used in for characterizing compound containing CH3CO or a group like CH3CH2OH which can be easily oxidised to CH3CO group by halogens. Illustration 14. Give a chemical test to distinguish between each of the following pair of organic compounds. (i) propanal an propanol (ii) propanone and propanal Solution: (i) Propanal is an aldehyde and gives a silver mirror with Tollens reagent while propanol is an alcohol which do not respond silver mirror test positively. (ii) (a) Propanone give yellow ppt. of iodoform on reaction with I2/NaOH while propanal does not react. (b) Propanal gives silver mirror with Tollens reagent while propanone does not.

14

Illustration 15. What is Fehlings solution? Solution: Fehling solution is a mixture of alkaline copper sulphate (Fehling A) and sodium potassium tartrate (Fehling B).

Exercise 19: How does the oxidation state of copper changes when Fehling solution is added to acetaldehyde? Exercise 20: Which of the following compound gives yellow precipitate with iodine and sodium hydroxide? (i) 3-methyl-4-phenyl but3en2one (ii) 1- phenyl ethanone (iii) Butanal (iv) Pentan3one 4. Reduction Carbonyl compounds can be reduced to 1 or 2 alcohol, by LiAlH4, NaBH4 or direct reduction with H2/Ni. (a)
LiAlH4 CH3 CHO CH3CH2OH LiAlH4 CH3 CH = CHCHO CH3CH 2CH 2CH 2OH

with LiAlH4 CHO group is reduced to CH2OH (1 alcohol) and C = C bond is also reduced when it is in conjugation with carbonyl groups.
O OH

LiAlH 4 H+

Group is reduced to

CHOH

(2 alcohol)

LiAlH4 also reduces ester & acid chloride to alcohols.

(b) NaBH4 has similar function. But this reagent does not affect (C = C) double bond.
OH
H2 / Ni

NaBH4 Ethanol

OH

NaBH4 does not reduce ester & acid chloride

CH2OH HO
NaBH 4 Ethanol

CHO O HO

CH2OH

LiAlH4

C2H5OH

COOC 2H5

COOC 2H5

CH2OH

(c) Amalgamated zinc, Zn(Hg) & conc. HCl (Clemmensen reduction) & hydrazine (NH2 NH2) followed by reaction with strong base like KOH in alkaline glycol (Wolf Kishner reduction) reduces carbonyl group to alkyl group.
C
NNH2 Wolf kishner
NH2 NH2

CH2 O Clemmensen reduction

Zn( Hg) + Conc.HCl / H2 O

Glycol, KOH

CH2

(d) Reduction to pinacol

CH3 CH3
Mg Hg, Benzene H3C 2CH3COCH3

CH3 CH3
H2 O CH3 H3C

C O

C O Mg

CH3

OH OH (pinacol)

Illustration 16. Find A and B:

CHO O
A or
Clemmensen Wolf Kischner H2 / Ni B

COOC 2H5

Solution:

CH3 HO A= B=

CH2OH

COOC2H5

COOC2H5

Illustration 17. Explain Clemmensens reduction. Solution: In Clemmensens reduction, we reduce the carbonyl group to CH2 using zinc amalgam in concentrated HCl.
C
H3C C
Zn / Hg O HCl

CH2
CH2 H Ethane

Zn / Hg H3C O HCl

H Ethanal

16

Illustration 18. Name the major product of the following reactions: (i) (ii)
Zn / Hg CH3CH = CH CH 2CHO HCl

H3C
N2 H 4 O KOH / glycol

H3C

Solution:

(i) (ii)

CH3 CH = CH CH 2CH3 ( Pent 2 ene )

H3C 1, 1 - dimethylcyclohexane H3C

Exercise 21: Convert propanone into propane.

Exercise 22: Write the structures of A and B.

2 4 A B OH 573K KOH / glycol

Cu

N H

Exercise 23: The reduction:

O OH

can be brought about by (A) LiAlH4 (C) Clemmensens reduction

(B) NaBH4 (D) WolffKishner reduction

Exercise 24: The appropriate reagent for the transformation:

O

CH3 HO

CH3 HO

(A) Zn Hg / HCl (C) Both (A) & (B)

(B) (i) NH2 NH2 (ii)OH (D) None of these

Exercise 25: Under Wolff Kishner reduction conditions, the conversion which may be brought about is
OH

OH

(A)

OH

(B)

OH

(C)

(D)

5. Reaction with Alkalies (A) Aldol Condensation Two molecules of an aldehydes or a ketone having atleast one - hydrogen atom, condense in presence of a dilute alkali to give a - hydroxyaldehyde or - hydroxy ketone.
O H3C C HCH2CHO dil. NaOH H3C OH C CH2CHO

H Ethanal

H ( 3- hydroxy butanal)

The products of aldol condensation when heated with dilute acids undergo dehydration to form , - unsaturated aldehydes or ketones.
OH H3CHC CH2CHO H3CHC CHCHO(crotonaldehyde) H2 O But-2-enal
H+ , heat

In general all aldehydes & ketones which contain - hydrogen can undergo this reaction. Those which do not contain - hydrogen like HCHO, C6H5CHO etc, do not undergo this reaction. Mechanism Mechanism involves formation of carbanions (i) a nucleophile form first molecules which is condensed with second molecule.
O OH H
O H 2C C H H2 C

O H
O C H

CH2

H2O

H2C

O H3C CH H2 C

O CH

O H3CHC CH2

O C H

18

O H3C CH CH2

O C H H2 O H3C

OH CH CH2 Aldol

O C H OH

Aldol product on dehydration give , - unsaturated ketones.

OH H3C CH CH2 O C H

H3C

CH

CH

CHO

Illustration 19. Convert ethanal into 2 butenal. Solution:

dil. N aOH CH 3CHO H3C

CH OH

Heat CH2CHO HCH3C H+

CHCHO

Exercise 26: base HCHO + CH3CHO Major product will be (A)

H3C OH OH

(B )

CHO HO

(C) HO Exercise 27:

O

CHO

(D )

None

H2C

+
O

CH3

1. OH X ( ultimate ). The product X is: 2.

(A)
O

(B )

O CH3

(C)

(D )
O
O

(B) Cannizzaros reaction Aldehydes that have no -hydrogen atom (or acidic hydrogen) undergo cannizzaro reaction (CR) in which disproportionation reaction takes place one being reduced to alcohol & other being oxidised to salt of the corresponding carboxylic acid. The reaction lakes place with 50% aqueous or ethanolic alkali solution.
2HCHO NaOH 50% Reduction Oxidation CH3OH HCOONa

2 ( CH3 ) 3 CCHO + NaOH ( CH3 ) 3 CCH 2OH + ( CH 3 ) 3 CCOONa

50%

When an aldehyde (showing CR) is treated with HCHO & 50% base, then HCHO undergo oxidation (rather than any other aldehyde). This reaction is called crossed CR.
CHO HCHO NaOH CH2OH HCOONa

CR involving different aldehydes or same aldehydes is proton (H+), hydride (H ) transfer reaction. Mechanism
O 2HCH 2NaOH HCH2OH O H CONa

Step I
OH H C H O OH H C H O

Step II
OH H C H HCOO O H H C O slow H OH C O H H C H HCH2OH O

When the reaction is carried out in D2O instead of in H2O, it is found that there is no new C D bond formation. This indicate that the hydrogen must come from aldehyde & not from the solvent. Illustration 20. Identify aldehydes which can give cannizaro reaction (CR): (a) CCl3CHO (c) (CH3)3CCHCl2 Solution: (b) (CH3)2CHCHO (d) C6H5CHO

Aldehydes which do not have H at - C give CR. (i) a & d do not H at - C hence give CR. (ii) b has H at - C but due to steric hindrance it gives CR. (iii) c with OH reactant is first converted to aldehyde which does not have H at - C hence give CR.

20

OH (CH3)3CCHCl2

(CH3)3C CH
OH

OH

H2 O (CH3)3CCHO

Exercise 28: Identify A & B in the following reactions:

dil . NaOH Sn ( Hg ) conc.HCl O A B

Exercise 29: Write the structure of A and B in the following reaction.

CHO
Heat dil . NaOH B CH 3 CHO A

Exercise 30:
OD /D2O PhCHO
-

Find product of the reaction. Exercise 31:

D D O ( 2 moles) + OH X +Y
( conc.)

where X and Y are: (A)

D O
-

O and

D H
D and

D OD
D OH

(B )

O H O
-

D and D

D OH

(C)
H

(D )

O D O
-

D and D

D OH

Exercise 32: In the Cannizzaro reaction given below:

Ph (A) (B) (C) (D)

OH Ph CH2OH CHO PhCOO the slowest step is The attack of OH at the carbonyl group The transfer of hydride to the carbonyl group. The abstraction of proton from carboxylic acid The deprotonation of Ph COOH.

(C) Perkin reaction In this reaction aromatic aldehyde is heated with an acid anhydride & its corresponding sodium salt to form condensation products which on hydrolysis gives , - unsaturated acids. Acetic anhydride & sodium acetate are commonly used in this reaction.
PhCHO (CH3CO)2O CH3COONa Ph CH CH COOH Cinnamic acid CH3COOH

6. Miscellaneous reactions (i) Formation of phorone Three moles of acetone condense in the presence of dry HCl to form phorone.
H3C 3 H3C C O dry HCl gas H3C -H2O H3C O C CH C CH C CH3 CH3

Phorone

(ii) Formation of mesitylene Three moles of acetone on refluxing with conc. Sulphuric acid produces mesitylene as one of the products.
CH3 H3C 3 H3C C
2 4 O 3H O 2

conc.H SO

H3C Mesitylene

CH3

(iii) Reaction with alc. KCN On heating with ethanolic solution of KCN, two molecules of aromatic aldehyde undergo condensation to form benzoin. It is called benzoin condensation.
O 2 benzaldehyde CH O
alc.KCN

OH CH

benzoin

(iv) Reaction with chloroform Ketones condenses with chloroform in presence of alkali to form chloretone.

22

H3C C H3C O CHCl3 KOH

H3C C

OH

CH3 CCl3

Illustration 21. Convert acetone into mesityl oxide. Solution:

H3C C CH3
2 H3C O

OH
dil. Ba( OH )

C CH3

Heat H3C CH2COCH3

C CH3

CHCOCH3

Exercise 33: What is trioxane? Give its structure.

ANSWER TO EXERCISES Exercise 1:

CHO

Exercise 2: The structure of diphenyl ketone is H O H

H H

H H

Number of sigma bonds = 25 Exercise 3: We remove aldehyde as soon as it is formed thus preventing its further oxidation to carboxylic acid. Exercise 4: A HOCH2 CH2 CH2 CHO
O B OHC CH2 CH2 C Cl

Exercise 5:
Cl H3C C CH
NaNH2 CH3 H3C

CH3

H2SO4 & HgSO 4 H3C C O CH2 CH3

Exercise 6: The hydrocarbon (A) is 2, 3 dimethylbut-2-ene.

H3C C C CH3

CH3 CH3

24

Exercise 7: (i) sp2 & sp3 respectively. (ii)

O O 2HCHO

Exercise 8: (A) Exercise 9: (A) Exercise 10: (C) Exercise 11:The angle (a) is 120 while angle (b) is 116.5, slightly less than 120. Exercise 12:The large value of the dipole moment of ethanal is due to larger contribution of the dipolar ion structure (II).
O O C (II)

H (I)

Exercise 13: The correct order of increasing boiling point is IV < II < III < I Exercise 14:
H3C H3C C H
O
NaHSO 3

ONa

H + ion

H3C H

OH SO 3Na

So 3H

Crystalline product

Exercise 15:(B) Exercise 16: The NH2 group labelled (b) undergo condensation with carbonyl group. The NH2 group (a) is involved in resonance with CO group and is deactivated.
O H2N C NHNH2 H2 N O C NHNH2

Exercise 17: (i) (ii)

NH2 CONHNH2 CH3 CHO CH3CH = NNHCONH 2 NH NH H3C ( CH 3 ) 2 CO
2 2

C CH3

NNH2

Exercise 18: (D) Exercise 19: Exercise20: (i) 3-methyl-4-phenyl but 3 en 2 one (ii) 1- phenyl ethanone Exercise 21: O
Zn / Hg CH3 CCH3 H3C HCl

The oxidation state of copper change from +2 to +1.

CH2 CH3

Exercise 22:
A O cyclohexanone B Cyclohexane

Exercise 23:(B) Exercise 24: (B) Exercise 25:(D) Exercise 26:(B) Exercise 27:(A) Exercise 28: Cyclohexanone undergoes aldol condensation in presence of dil. NaOH.
O O

O H

OH
OH (A)

Sn(Hg) conc.HCl

OH (B)

26

Exercise 29:
A CH OH
B O

CH2 CHO

Exercise 30:
OD O

Ph H

Ph

Exercise 31:(D) Exercise 32:(B) Exercise 33: Trioxane is a cyclic trimer of methanal. Its structure is
O H 2C O CH2 O CH2

MISCELLANEOUS EXERCISES Exercise 1: Exercise 2: Exercise 3: Give the industrial preparation of ethanal. Write an equation for making aldehydes by the oxo process. What happens when ethanal reacts with excess of methanol in the presence of trace amount of dry HCl? Convert acetic acid into acetaoxime. Give some physical properties of acetone. Which aldehyde smells like bitter almonds? Give its one use. Give one difference between the paraldehyde and metaldehydes. What type of aldehyde undergo cannizzaro reaction? What happens when ethanal is distilled with dilute H2SO4 at 273 K? What is formalin? Give its one use.

Exercise 4: Exercise 5: Exercise 6: Exercise 7: Exercise 8: Exercise 9: Exercise 10:

28

ANSWER TO MISCELLANEOUS EXERCISES Exercise 1: Wackers process CH2 = CH 2 + Exercise 2: 1 Pd Cl2 O 2 CH3CHO CuCl2 2

Alkene on reaction with (CO + H2) in the presence of dicobalt octacarbonyl as a catalyst giving an aldehyde with one carbon more.
2 8 RCH = CH2 + CO + H2 RCH2CH 2CHO

Co ( CO )

Exercise 3:

H3C

CH O

H OCH3 H OCH3
HCl HCH3C

OCH3 OCH3

1, 1 - dimethoxyethane

Exercise 4:

H 2NOH 2 CH3 COOH CH3COCH3 dry distill HCl

Ca ( OH)

H3C

C CH3

NOH

Exercise 5:

(i) It is a colourless, pleasant-smelling liquid. (ii) It is miscible in water. Benzaldehyde smells like bitter almonds. It is used in perfumes. Paraldehyde is a cyclic trimer of CH3CHO and is a pleasant smelling liquid. Metaldehyde is a cyclic tetramer of CH3CHO and is a white solid. Aldehyde without -hydrogen atom undergo cannizzaro reaction. Example, HCHO,

Exercise 6: Exercise 7:

Exercise 8:

Exercise 9: Exercise 10:

Ethanal form metaldehyde (cyclic tetramer of ethanal). 40% aqueous solution of formaldehyde is called formalin. It is used as a disinfectant.

SOLVED PROBLEMS Subjective: Board Type Questions Prob 1. Arrange the following compounds in increasing order of their reactivity in nucleophilic addition reaction: Benzaldehyde, p tolualdehyde, p nitrobenzaldehyde, acetophenone. Acetophenone is ketone, all other are aldehydes, it is less reactive. +M group increases electron density and so makes the compound unfit for nucleophilic addition & vice versa is true for M group. Order is: Acetophenone < p tolualdehyde < benzaldehyde < p nitrobenzaldehyde Identify A, B & C in the following
CH3 MgBr

Sol.

Prob 2.

NBS NaCN B A

C H O
3

Sol.

CH3

CH2Br

CH2CN

NBS allylic substitution

NaCN SN

(A)

(B) MgBr

O H 2C C H 3O

(C)

Prob 3.

Complete the following: O (i)

CH3 CH3

NaOCl

(ii)
O 2N

O C
NaOI CH3

30

(iii)
H3C CH

O CH2 C CH3

I2 / NaOH

Sol.

(i)

CH

CH CH3

COONa

CHCl3

(ii)

O 2N

COONa

CHI3

(iii)

H3C

CH

CH2 COONa

CHI3

Prob 4.

What is the final product of?

OH , O

Sol.
O
O

OH

H 2O

O O

O H2 O OH

Prob 5.

Arrange the following in increasing extent of hydration:

O O Br CHO CHO Br

Sol.

The extent of hydration increases as groups tendency to form H bonding increases. In general hydration of an aldehyde is greater than that of a ketone.
O O Br < < < CHO CHO Br

Prob 6.

Identify A, B & C in the following

O Pt, 1 equ. H 2 A

Raney Ni, H2 NaBH4, CH 3OH

B C

Sol.

With Pt, only double bond is affected

O
A is

With Raney Ni,

O C
||

groups as well as double bond is reduced.

OH

B is

NaBH4, CH3OH does not reduce double bond.

OH C is

Prob 7.

Compound A, having the empirical formula C7H8 is chlorinated in sunlight to give a product which is hydrolysed to produce B. B after oxidation reacts with acetic anhydride in the Perkin reaction to produce an acid C, which has an equivalent weight of 148. Give the name & structure of A, B & C.

32

Sol.

Since B on oxidation undergoes Perkin reaction, the oxidised compound is benzaldehyde & A is toluene.
CH3 CH2Cl CH2OH

2,h Cl
(A)

2 O / OH H

(B) Oxidation

HC

CHCOOH

CHO

Perkin reaction
(C)

Prob 8.

Which of the following ketone is more acidic? Give a reason.

O O

Sol.

O Base

This ketone is more acidic because the resulting enolate ion obeys Huckels rule & is thus more stable. Prob 9. Sol. Prob 10. Explain why acetophenone but not benzophenone forms an adduct with NaHSO3. Because of steric hinderance of two phenyl groups. Which of the following compound gives positive iodoform test? (a) 2 butanol (b) 1 pentanol (c) Acetone (d) 3 pentanone Compounds containing O C CH3
||

Sol.

&

C HCH3
OH
I

will give a positive iodoform test.

2 butanol & acetone will give positive iodoform test. Prob 11. Suggest a chemical test that will distinguished the following pairs of compounds (a) Acetic acid & propanal (b) Acetaldehyde & acetone (a) Propanal gives Tollens test. (b) Acetaldehyde gives Tollens test.

Sol.

Prob 12.

Complete the following reaction by giving the principal organic product.

Br

HOH / H C6 H5CHO 2Mg / ether B A 2 moles

Cl

Sol.
Br MgBr (i)
ether 2Mg /

CHO HOHC C6 H5

Cl (A)

(i) HOH/H MgCl (B)

CHOH-C6H5

Prob 13.

Starting with cyclohexanone suggest reasonable synthesis for the following:

D D O

D
D D O D2O/OH O

Sol.

Prob 14.

With in each pair which compound will react faster in carbonyl addition reactions: (a)
O O or

(b)
CHO or

O C CH3

Sol.

(a) Cyclopropanone (b) Benzaldehyde

34

Prob 15.

Complete the following reaction:

CHO

HCHO

KOH

OCH3

Sol.

CH2OH

Products =

HCOO K

OCH3

Objective: Prob 1. The correct order of reactivity towards nucleophilic addition reaction will be (A) CH3CHO > ( CH 3 ) 2 CO > CH 3COC 2H 5 (B) ( CH3 ) 2 CO > CH 3CHO > CH 3COC2H 5 (C) CH3COC2 H5 < CH 3CHO > ( CH 3 ) 2 CO (D) CH3CHO < CH 3COC2 H 5 > ( CH 3 ) 2 CO Sol. Aldehydes are more reactive than ketones due to lesser number of +I group & again the reactivity of carbonyl group depends on the major nature of alkyl group attached to it. So correct order is CH3 CHO > ( CH3 ) 2 CO > CH3COC 2H5 (A) Prob 2. Which of the following will not give aldol condensation? (A) RCH2CHO (B) RCOCH2R (C) C6H5CHO (D) C6H5CH2CHO Aldol condensation is given by those carbonyl compounds, which possess at least one - H. Q (C) is not having hydrogen hence it will not give aldol condensation (C) Aldehydes & ketones can be reduced to corresponding hydrocarbons by (A) refluxing with strong acids (B) passing the vapours under heated PbO2 (C) Refluxing with zinc amalgam (D) Refluxing with strong alkali (C) Which of the following compound gives a positive iodoform test? (A) pentanal (B) 1 phenyl ethanol (C) 2 phenyl ethanol (D) 3 pentanol Haloform test is used to identify COCH3 group or CH3 CH(OH) group which can O || be oxidised to . 1 phenyl ethanol will give this test. CH3 C (B) Prob 5. Which of the following compound will give Cannizzaros reaction? CH3 | (A) CH3CH2CH2CHO (B) CH3CH2 CH CHO (C) (CH3)2CHCH2CHO Sol. (D) (CH3)3C. CHO

Sol.

Prob 3.

Sol. Prob 4.

Sol.

The compounds which do not contain - hydrogen atom undergo cannizzaros reaction. (D)

36

Prob 6.

Compound A(C6H10O) form a phenyl hydrazone and gives a negative Tollens reagent test & iodoform test. On reduction with Zn/Hg, HCl compound A gives n pentane. A is (A) 1 alcohol (B) aldehyde (C) 2 alcohol (D) ketone As A forms phenyl hydrazone it must be a carbonyl compound again, it is giving negative test with Tollens reagent test, it is a ketone. (D) The end product of the reaction is
NBS

Sol.

Prob 7.

X
COCH3

( ) 3 Mg / ether Y Z ( ii ) H2O
i CH CN

(A )

(B)
CO COOH

(C )

(D)
COCH2OH

none

Sol.

Br

Mg

Br

NBS

ether
Mg
(i) CH 3CN (ii) H 2O

CO

CH3

(A) Prob 8. Arrange the following compounds in order of their decreasing activity towards Tollens reagent: HCHO CH3CHO CH3COCH3 C6H5CHO I II III IV (A) I > II > IV > III (B) I > II > III > IV (C) II > I > III > IV (D) none Aldehydes are more reactive than ketones (A)

Sol.

Prob 9.

The most reactive compound towards formation of cyanohydrin on treatment with KCN followed by acidification is (A) benzaldehyde (B) p nitrobenzaldehyde (C) phenylacetaldehyde (D) p hydroxybenzaldehyde Presence of electron withdrawing group in para position increases nucleophilic addition. (B) Which of the following chemical system has most acidic hydrogen? (A) 3 hexanone (B) 2, 4 hexanedione (C) 2, 5 hexanedione (D) 2, 3 hexanedione 2, 4 hexanedione has CH2 group surrounded on both sides of electronegative (>C=O) group, hence it is acidic in nature, the carbanions
O H3C C CH O C CH2CH3

Sol.

Prob 10.

Sol.

, once formed stabilizes due to resonance.

(B) Prob 11. Predict the product B in the sequence of reaction:

3% H2 SO4 NaOH CH CH A ( B) Hg 2 +

(A) (C )

CH3COONa CH3CHO

(B ) (D )

CH3COOH
CH3 CH OH CH2CHO

Sol. Prob 12.

H2 SO4 NaOH CH CH CH3 CHO CH3CH ( OH) CH 2CHO Aldol condensation Hg2+

(D) Acetophenone can be prepared by (I) Oxidation of 1 phenylethanol (II) Reduction of benzaldehyde with methyl magnesium bromide (III) Friedel crafts reaction of benzene with acetylchloride (IV) Distillation of calcium benzoate Which of above is correct? (A) I & III (B) II & IV (C) III & IV (D) I & II
AlCl3 [O] C6H5CHOHCH3 C 6H5COCH3 C 6H 6 + CH 3COCl

Sol. Prob 13.

(A) An organic compound A has the molecular formula C3H6O. It undergoes iodoform test. When saturated with HCl it gives B of molecular formula C9H14O, A & B respectively are (A) propanal & mesitylene (B) propanone & mesityl oxide (C) propanone & 2, 6 dimethyl 2, 5 heptadien 4 one (D) propane & meistylene oxide Since the compound A has the molecular formula C3H6O & undergoes iodoform test, it should be CH3COCH3. Further reaction of B with HCl gives C9H14O, this should be trimer of acetone, i.e. It should be phorone.

Sol.

38

Prob 14.

(C) What will be the product when 2-Butenal reacts with sodiumborohydride? (A) Butanal (B) Butanol (C) But-2-ene-1-ol (D) None (C) Which will give a yellow precipitate with iodine & alkali? (A) 2 hydroxyl propane (B) benzophenone (C) o methyl toluene (D) acetamide (A)

Sol. Prob 15.

Sol.

ASSIGNMENT PROBLEMS Subjective: Level O 1. Suggest a reason for large difference in the boiling points of butanol and butanal, although they have same solubility in water. 2. Arrange the following in order of their increasing reactivity towards HCN? CH3 CHO, CH3COCH3 , HCHO, C 2H5COCH3 3. To what oxidation state does ethanal reduce Cu (II). 4. Write the I.U.P.A.C. name of
OH CH3 CH CH2 O C CH3

5. Identify A, B and C:
O CH3C
Ca(OH)2 NH2 . NH2 OH A B C

6. Complete the following reaction:

CHO

+ NaOH

7. Find the product:

OH H3C CH CH2 CO CH3

8. Give the equation associated with Fehlings Test given by CH3CHO. 9. How will you convert acetone into 2 methyl 2 propanol? 10. Mention an industrial product manufactured from methanal. 11. Account for the following: (i) In the reactions of aldehyde/ketones with ammonia derivative, the pH has to be carefully controlled. (ii) There are two NH2 groups in semicarbazide. However, only one is involved in the formation of semicarbazones. (iii) Cyclohexanone forms cyanohydrin in good yiled but 2, 2, 6 trimethyl cyclohexanone does not.

40

12. Effect the following conversions: (a) Acetone to propyne (b) Acetaldehyde to acetaldehyde semicarbazone. 13. Give one chemical test to distinguish following pair of compounds in solution: Acetone and acetaldehydes. 14. Give one chemical test to distinguish : Acetaldehyde and benzaldehyde. 15. Write the equations and conditions to show how the following conversions are carried out: (a) Benzaldehyde to acetophenone (b) Acetaldehyde to 2 Butenal

Level I 1. Arrange the following in order of decreasing acidity:

CH2CH2CHO CH2CH2CHO

CH3 CHCHO NO2 Cl (II)

(I)

(III)

2. The following ketone is unusually basic. Explain.

O

3. Name the alkyne which can give the following carbonyl compounds on acid catalysed hydration. O O (i) (ii)

(CH3)3CCCH3
4. Which alkene would give the following products on ozonolysis?

CH3

O OHC

HCHO

5. Complete the following reaction

O

HCN

6. Explain why only -hydrogen atom in aldehydes & ketones is involved in the aldol condensation.

42

7. Which of the following compound gives a positive iodoform test? 2 pentanone & 3 hexanol 8. Arrange the following compounds in order of increasing reactivity towards the addition of HCN. Acetone, acetaldehyde, methyl t butyl ketone & di t butyl ketone. 9. Show the product of following reaction
NH2 O NH2 O C C H H
H2O NaHSO4

10. Identify products when PhCOCHCl2 undergoes Cannizzaro reaction: 11. Give the aldol condensation product of: (a) CH3CH = CHCHO (b) Mixture of
CH CHCHO & CH3CH CHCHO

12. What happens when cyclopentanone is treated with ethyl magnesium bromide & the product is hydrolysed? 13. What starting compound would you use in an aldol cyclisation to prepare each of? O (a) (b)

CH3

14. What reagents would you use to carry out following reactions? Ethyl bromide 1-butyne 2 butanone 15. Arrange the following in increasing extent of hydration: O O O H
CH3C CH3 , CH3 C CH2Cl , H3C C

O , ClCH2 C H , HC H

Level II 1. Identify the product of (i)

CHO O C CH3
, OH

(ii)
O

OH ,

2. Complete the following reaction:

HC CH CH3MgBr X
CH4

CO2 Z Y H O+
3

HgSO4 + H2 SO4

KMnO4

3. Write the final product of

H3O O O

4. Complete the following reaction: O O

() 3 CH3C CH2 CCH2CH3 ( ii) H3 O+ (excess)
i CH MgBr

5. Identify A, B & C in the following

O

H LiAlH O A C B
4

6. Complete the following reaction: HCl CH 3 CH2COCH2CH3 + CH3CH2ONO X gas 7. Show the mechanism of following reaction:
O O H HCl H H Cl

44

8. Supply the structure from A to E:

CH3 CH2MgBr H3O H2 Pt

A B

O PhCH CHCCH3

NaBH4 H

LiCu(CH3 )2 H O3 Zn/H

9. Effect the following conversion: O O (a)

(b)

O CH2CH2CCH(CH3)2 O

10. How will you bring about the following conversions in not more than two steps? (i) Propanone to propene (ii) Propanal to butanone (iii) Benzaldehyde to benzophenone (iv) Ethanol to 3-hydroxybutanal (v) Benzaldehyde to 3 phenyl propan 1- ol (vi) Benzene to m-Nitroacetophenone 11. Illustrate the mechanism of reaction of carbonyl group with an ammonia derivative, H2NZ. 12. Give simple chemical test to distinguish between the following pairs of compounds: (i) Propanal and propanone (ii) Ethanal and propanal (iii) Propanal and Diethyl ether (iv) Propanone and propanol 13. Explain haloform reaction. 14. An organic compound with the molecular formula C9H10O form 2, 4-DNP derivative, reduces Tollens reagent and undergo Cannizzaro reaction. On vigorous oxidation, it gives benzene-1, 2- dicarboxylic acid. Identify the compound and write the reactions involved. 15. Compound A on treatment with PCl5 gives compound B which on reduction with H2 / Pd in presence of BaSO4 gives compound C. C gives Tollens test, Fehlings test and iodoform test. When C is treated with dil. NaOH, D is obtained, which on heating gives crotonaldehyde. Identify A, B, C, D and complete sequence of reaction.

Objective: Level-I 1. Polarization of electrons in acrolein may be written as: (A) CH2 = CH CH = O (C) CH2 = CH CH = O
+ + +

(B) CH2 = CH CH = O (D) CH2 = CH CH = O

+

2. Which reagent will perform the following reduction? CH3 CH = CH CHO CH3 CH = CH CH 2O H (A) LiAlH4 (C) H2/Ni 3. The ketone that does not form a cyanohydrin is (A) C6H5COCH3 (C) C6H5COC6H5 (B) CH3COCH3 (D) CH3COC6H5 (B) NaBH4 (D) Mg/Hg + H2O

4. The decreasing order of solubility of methanal (I), propanaldehye (II), benzaldehyde (III) & acetophenone (IV) is (A) I, II, III, IV (B) IV, III, II, I (C) IV, I, II, III (D) II, I, III, IV 5. Which of the following compounds will undergo self aldol condensation in presence of dil. alkali? (A) C6H5CHO (B) CH C CHO (C) CH3CH2CHO (D) CH2 = CHCHO 6. Which of the following does not undergo benzoin condensation? (A)
CHO

(B)

CHO

OCH3

(C)

CHO

(D)

C6H5CH2CHO

CH3

46

7. In the reaction
CH3CH2 C H O

() 2 4 X ( ii ) LiAlH 4
i HCN / H SO

What is X? CH3CH2 CHCH2NH2 (A)

(B)

CH3CH2CH2CHCH2NH2 OH

OH
(C)
H3C CHCH2CH2CH3 OH

(D)

CH3 CH3CH2C OH NH2

8. Identify the final product Z in the following sequence of reaction:

H3 O H2 SO 4 Me2C = O + HCN [ X] Y Z
+

(A) (CH3)2C(OH)COOH (C) HO CH2CH(CH3)COOH

(B) CH2 = C(CH3)COOH (D) CH3CH = CHCOOH

9. A dihalo alkane on hydrolysis produces a ketone with formula C3H6O. The dihalo alkane is (A) 2, 2 dichloropropane (C) 1, 2 dichloropropane (B) 1, 1 dichloropropane (D) 1, 3 dichloropropane

10.

ON2

LiAl(O Bu i)3 COCl A, A can be

(A)

CHO

(B)

H2 N

COCl
O

(C)

ON2

CHO

(D)

ON2

CH3

11. Identify X in the sequence K 2 Cr2 O7 I2 + NaOH X C3H6 O CHI3 H2 SO 4 water (A) CH3 CH2 CH2OH (B)
H3C CH OH CH3

(C) 12.

CH3 O CH2CH3
O

(D)

CH3 CH2CHO

H3C CH3

HCl + 2CH3OH A, where A is

(A)
H3C H3CO

CH3 OCH3

(B) An acetal

(C)

Propanaldehyde dimethyl acetal

(D)

All the above

13. Aldol condensation will not be observed in (A) Chloral (C) Hexanal 14. Greatest amount of hydration is in (A)
O

(B) Phenyl acetaldehyde (D) None of these

(B)

O Br

(C)

O C Br H

(D)

All are equal

15. Identify Z in the series Na2 CO3 HBr hydrolysis CH2 = CH2 X Y Z I2 excess (A) C2H5I (C) CHI3 (B) C2H5OH (D) CH3CHO

16. The product (s) obtained via Oxymercuration (HgSO4 +H2SO4) of butyne - 1 would be (A) (C)

CH3
CH3

CH2 COCH3
CH2 CHO CH2O

(B) (D)

CH3 CH3

CH2 CH2 CHO CH2 COOH HCOOH

17. Which one of the following reactions can not be used for the reduction of R R
C R O R CH2

48

(A) Clemmensen reduction (B) Wolf Kishner reduction (C) Wurtz reaction (D) HI and red phosphorous at 2000C. 18. An organic compound C3H6O does not give a precipitate with 2, 4 dinitro phenyl hydrazine and does not react with metallic sodium. It could be (A) CH3CH2CHO (B) CH3COCH3 (C) CH2 = CH CH2OH (D) CH2 = CH OCH3 19. A ketone reacted with Grignard reagent followed dehydration gave an alkene. The alkene on acetaldehyde. The ketone is (A) Dimethyl ketone (C) Diethyl ketone 20. Iodoform test is applicable for O (A)
H CH3
O

by hydrolysis gave a product which on ozonolysis gave diethyl ketone and (B) Ethyl methyl ketone (D) Ethyl isopropyl ketone

(B)
H3C

CH3

(C)

(D)

All the above

CH3

Level II 1. Acetaldehyde reacts with (A) electrophiles only (C) free radicals only (B) nucleophiles only (D) both electrophiles & nucleophiles

2. Aldehydes & ketones give addition (not condensation) reactions with (A) hydrazine (C) semicarbazine
H O NaCN B ( CH3 ) 2 CO ( HCl) A
3 +

(B) phenyl hydrazine (D) hydrogen cyanide

3.

In the above sequential reactions A & B are (A) (CH3)2C(OH)CN, (CH3)2C(OH)COOH (C) (CH3)2C(OH)CN, (CH3)2CHCOOH (B) (CH3)2C(OH)CN, (CH3)2C(OH)2 (D) (CH3)2C(OH)CN, (CH3)2C=O

4. In which of the following reactions, aldehydes & ketones are distinguished (A) reactions with phenyl hydrazine (B) reactions with hydroxylamine (C) reactions with semicarbazide (D) reactions with silver nitrate mixed with ammonia 5. The most probable structural formula for the compound whose empirical formula is C 3H6O & which can react with Benedict reagent is (A)
CH3CH O CH2

(B)

CH3CH2CHO

(C)

CH3OCH = CH2

(D)

CH2 = CHCH2OH

6. Base catalysed aldol condensation occurs with: (A) propionaldehyde (C) both (B) 2 methyl propionaldehyde (D) none

7. Aromatic aldehydeso undergoes disproportionation in presence of sodium or potassium hydroxide to give corresponding alcohols & acid. The reaction is known as (A) Wurtz reaction (C) friedel crafts reactions (B) cannizzaro reaction (D) claisen reaction

50

8.

CHO

OHC

() Major prodcut is ( ii) H+ / H O

i NaOH /100 0 C
2

CHO

(A)

OHC COOH HOOC

(B)

OH HOOC

HOOC COOH

HO COOH

(C)

(D)
O

CH2OH HOH2C

O
O

HOH2C CH2OH

9. Compound A (molecular formula C3H8O) is treated with acidified K2Cr2O7 to form a product (B) (molecular formula C3H6O). B forms a shining silver mirror on warming with ammoniacal AgNO3. B when treated with an aq. Solution to H 2NCONHNH2, HCl & Sodium acetate gives a product C. Identify the product C. (A) CH3CH2CH = NNHCONH2
H3C C CH3 NCONHNH2
H3C C CH3 NNHCONH2

(B)

(C)

(D)

CH3CH2CH = NCONHNH2

10. In a cannizzaro reaction, the intermediate that will be best hydride donar is (A)
H O OH

(B)

H O O

(C)

H O O OMe

(D)

H O O O 2N

11. Mixture of CH3CH2OH & CH3CHO can be separated by using (A) NaHSO3 (C) HCN
O

(B) NH2OH (D) NH2 NH2

12.
COCH3 CH3
O

() ( ii) H+
i KOBr,

Y, Y is

( iii )

(A)
COOH CH3

(B)
CH3

(C)

COOH

(D)

COOH CH3

OH

OH

13.
CHO
2 Cl 2 X,

H O

CHCl3 Br2 Y

X and Y are
O
O

(A)
Cl CHO Br ,

(B)

CHO

Cl

Br

OH

(C)
Cl CHO , Br

(D)

None is correct

52

14. Following is hydrated maximum at the position:

O
1 2 3

(A) 1 (C) 3 15.

H3C C O CH2 CH2 CH2 C O
O H3C C H3C C C CH2 CH2

(B) 2 (D) equal

CH3
OH ,

A is (A) (B)
H3C O C H3C C CH CH CH2

(C)
H3C

O C H3C CH CH CH CH

(D)

None is correct

CrO3 , pyridine HBr alc. KOH HBr aq. KOH A B C D E 16. RCH = CH2 Peroxide CH2 Cl2

In above conversion E can be (A) Propanol (C) Pentanal

(B) Butanal (D) Both (B) and (C)

17. Identify the final product (Z) in the following sequence of reactions.
dil. KMnO4 HIO4 OH (X) (Y) (Z)

(A)

OH OH

(B)
O

OH

(C)
O

(D)
O

18. The conversion; CH3CH=CHCHO CH3CH=CHCOOH can be effected by (A) alk. KMnO4 (B) K2Cr2O7/H+ (C) ammoniacal AgNO3 (D) SeO2

19. The abstraction of proton will be fastest, in which carbon in the following compound,
O y x H3C z p CH3

(A) x (C) z 20. Which of the following will be most acidic?

O

(B) y (D) p

(A)
CH3

(B)
CH3
O

(C)
H3C CH3

(D)

H3C CH3

CH3

54

ANSWERS TO ASSIGNMENT PROBLEMS Subjective: Level O 1. Butanol undergoes hydrogen bonding but butanal does not. 2. C2H5 COCH3 < CH3COCH3 < CH3CHO < HCHO

3. +1 oxidation state. 4. 4 Hydroxypentan 2 one 5. A = (CH3 COO)2 Ca

B = CH3 C O CH3

C = (CH3 )2 C = NNH2 6.
CH2OH COONa

7. 8. 9.

H3C

CH

CH

CO CH3

CH3 CHO + 2CuSO 4 + 4NaOH CH3COOH + Cu 2O + Na 2SO 4 + 2H 2O Red ppt.

O CH3 C
CH3 MgBr H 3O CH3 CH3
+

OH C CH3 CH3

10. Bakelite. 11. (i) The reaction

OH C O + H 2N Z C NHZ
H 2O C

Z is pH sensitive.

At lower pH (solution is highly acidic), the protonation of N takes place thereby decreasing the concentration of free base available.
+ + NH2 +H H 3N Z

The H3N+ Z can not attack now at the carbonyl carbon. At higher pH, (solution is basic), the base will remove H+ ion from OH in the intermediate formed thereby slowing the dehydration step.

(ii) In semicarbazide, the NH2 group closer to the

C = O
|

group is resonance stabilized

and is deactivated (lone pair of N is involved in resonance) compared to the other end NH2 group).
O H2NHN C NH2 O HNNH2 C NH2

deactivated

(iii) 2, 2, 6 trimethyl cyclohexanone does not form cyanohydrin as the carbonyl carbon is highly crowded and the electron density is very high due to the presence of three e donating methyl groups.
OH
HCN O

CN

H3C

CH3
HCN no reaction O

CH3

12.

(a)

CH3

C O

SOCl2 CH3 CH3

NaNH2 CH3

CH3

C CH Propyne

Cl 2, 3 - dichloro propane
H O H2N. NH C
H NH2 CH3
+

Cl

(b)
CH3

H C

N.NHCNH2 O

O Semicarbazide

13. Acetaldehydes on warming with Fehlings solution gives red precipitate of copper oxide, where as acetone does not. CH3 CHO + 2Cu(OH)2 + NaOH RCOONa + Cu 2O + 3H 2O (Red ppt.) 14. These two compounds can be distinguished by Fehlings test. Acetaldehyde gives red coloured ppt. with Fehlings solution but benzaldehyde does not. 15. (a)
CHO COOH
Alk. KMnO 4

COCl

COCH3

SOCl2

Cd(CH3 )2

Benzoic acid

(b)

OH
dil. NaOH CH2CHO 2CH3 CHO CH3CH CH3 CH = CHCHO Aldol 2 - Butenal

56

Level I 1. III > II > I 2. The salt of ketone is resonance stabilized.

O OH OH

etc

3. (i) (ii)

(H3C)3C

C
C

CH
CH

4.

5.

HO

CN

6. Because an -hydrogen atom is acidic & the resulting enolate anion is stabilized by resonance. 7. 2 pentanone 8. di t butyl ketone < methyl t butyl ketone < acetone < acetaldehyde. 9.
N

10.

COCHCl2

COCH(OH)2

COCHO

KOH

OH

O C

O C O
-H

O C

O C OH H

OH CH COO

11. (a)

CH3CH

CHCHO H

CH2CH

CHCHO
H2O

CH3CH

CHCH

CH CH

OHC
(b)
CH CHCHO & H2CH CH

CH

CHCHO

(CH=CH)3CHO

12.

O HO
CH3 CH2MgBr H O+
3

CH2CH3

13. (i) (ii)

CH3 C CH2CH2 C CH3 || || O O CH3 C CH2CH2CH2CHO || O

58

14.

CH3CH2Br

HC

CNa

CH3CH2C

CH

HgSO 4 /H 2 SO4

O CH3CH2CCH3

15.

H C

CH3C CH3 < CH3C CH2Cl < H3C

O < ClCH2 C H < HC H

Level II 1. (i)

O CH CHC

(ii)

2.
X = HC C HC MgBr +
CO2 H3 O

O C Y COH

Hg2 + , H2 SO 4

COOH H 2C COOH
KMnO4

CH

CH2 COOH

HO

HC

CHCOOH

3.

H 3O O O HO HO OH

-H2O OH HO O H OH

4.

OH

CH3C CH2CH2 C CH2CH3

() 3 ( ii ) H O +
i CH MgBr
3

CH3 CCH2CH2 CCH2CH3 CH3 cyclisation

H3C H3C

OH

CH3

5.

H3C OH

H3C

H3C

O (A)

(B)

HO

(C)

CH3CH2Cl + HONO 6. CH 3 CH2ONO + HCl

CH3COCH2CH3 +O = N OH CH3 COCCH3 NOH (X) oxime

60

7.

O H H Cl
-Cl

H H

H H

O H H Cl

Cl

8.
A = PhCH

OH

OH

O
CHCCH2CH3 CH3

C = PhCH

CHCCH3 H

B = PhCH2CH2 CCH3

O D = PhCHCH2 CCH3 CH3

E = PhCHO

O HC

O C CH3

9.

(a)

( ) ( iii ) H2O 2
ii PhSeBr

( i) LDA

H2 C = CHCH = CH2

H2 Pt O

(b)

O CH2CH2C CH(CH3)2
() 2 ( ii ) H2C =CHC CH ( CH3 )
i R NH, H
|| O + 2

(iii) H3O

10.

(i)
H3C

O C
L iAlH 4 CH3

OH H3C
OH CHCH3 Heat O
conc. H 2SO 4

H3C

CH

CH2

(ii)

Cu CH 3MgBr CH3CH2 C CH3 CH3CH2CHO CH3CH2 CHCH3 573k H+

(iii)

CHO

OH MgBr
H
+

O
PCC

CH

(iv)

| Cu dil.NaOH CH3 CH2OH CH CHO CH C HCH 2CHO 3 3 573K

OH

(v)

CHO

dil.NaOH +CH 3CHO Heat

CH

CH

CHO 600 C

H 2 / Ni

CH2CH2CH2OH

(vi)

NO2

NO2

HNO3 H 2SO4

3 2 AlCl 3

( CH

CO) O

COCH3

11. The reaction of carbonyl group with H2N Z is an acid catalysed reaction.
OH C O C
H 2N Z OH

C N H H -H OH Z

H + H 2O

C N Z

(i)

Test (a) Tollens reagent (b) Iodoform test (I2/NaOH)

Propanal (CH3CH2CHO) Silver mirror ve

CH3COCH3 (Propanaone) ve test Yellow ppt.

(ii) Test

Ethanal
O H3C C H

Propanal CH3CH2CHO ve test Diethyl Ether CH3CH2OCH2CH3 ve test ve Propanol CH3CH2CH2OH

Iodoform test (I2/NaOH) (iii)

Yellow ppt. Propanal CH3CH2CHO Silver mirror Reddish brown ppt. Propanone CH3COCH3

Test (a) Tollens test (b) Fehlings test

(iv)

Test

62

Iodoform test
O

Yellow ppt.

ve test

13. Methyl ketones

H3C

on oxidation with X2/NaOH (X = Cl, Br, I) gives sodium salt of

carboxylic acid with one carbon atom less. The CH3 group bonded to carbonyl group is converted to haloform, CHX3. With iodine in NaOH, a yellow precipitate of Iodoform CHI3, is obtained. (Iodoform test). X2 + 2NaOH NaOX + NaX + H2O
O H3C C
3NaOX R H3C

O C R 3NaOH

O CX3 C
NaOX R CHX3 + RCOONa

14. The compound is a carbonyl compound (+ve, 2, 4 DNP test) The carbonyl group is an aldehyde (+) ve Tollens reagent. The aldehyde group is directly bonded to benzene, no - H (Cannizzaro reaction). The other side chain is at the ortho position as it gives phthalic acid on oxidation. Hence the compound is
CHO

C 2H 5

The reactions are

C 2H 5 2,4 DNP

O 2N CH NNH NO2

C2 H 5 CHO Ag ( NH 3 ) 2
+

COOH C 2H 5 C 2 H5

C2 H 5

conc. NaOH

COONa

CH2OH

( O)

COOH

COOH

15.

CH3C O (A)

OH CH3
PCl5

C O (B)

Cl CH3
H2 / Pd BaSO4

C O (C)

NaOH OH CH3 CH CH
CHO CH3

CH (D)

CH2CHO

Crotonaldehyde

64

Objective: Level - I 1. 4. 7. 10. 13. 16. 19. Level - II 1. 4. 7. 10. 13. 16. 19. B D B D A D A 2. 5. 8. 11. 14. 17. 20. D B B A B B A 3. 6. 9. 12. 15. 18. A C A B A C D A A C A A C 2. 5. 8. 11. 14. 17. 20. B C B B C C D 3. 6. 9. 12. 15. 18. C D A D C D