ANSWER SCHEME TUTORIAL SK025 SEMESTER 2

SK025
CHAPTER 9.0: CARBONYL COMPOUNDS

CHAPTER 9.0 : CARBONYL COMPOUNDS UNIT 9.1: INTRODUCTION

UNIT 9.2 : NOMENCLATURE
LEARNING OUTCOMES:
9.1: INTRODUCTION TO CARBONYL COMPOUNDS
a) Give the general formula of aldehydes (RCOH) and ketones (RCOR).
9.2: NOMENCLATURE OF CARBONYL COMPOUNDS
a) Draw the structures and name aldehydes and ketones (parent chain ≤ C10) according to the IUPAC nomenclature.

TUTORIAL QUESTIONS :

1. Give the IUPAC name for each of the following aldehydes and ketones:

ANS:
CH3 CH2 CH2 C O butanal
(a)
H
CH3 2-methylbutanal
(b) CH3 CH2 CHC O
H
Cl CH3 4-chloro-2,4-dimethylhexanal
(c) H3C C CH2 C C O
CH2 CH3 H H
Br 3-bromo-4-methyl-2-pentanone
(d) CH3 CH CHC O
CH3 CH3
O 3-methyl-2-butanone
(e) CH3 C CH CH3
CH3
2-hexanone
CH3 CH2 CH2 CH2 C O
(f)
CH3
cyclohexanone
(g) O

phenylethanone @ acetophenone
(h) C O
CH3
(i) 1-phenyl-2-propanone
CH2 C O
CH3

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CHAPTER 9.0: CARBONYL COMPOUNDS
2. Draw the structural formulae and give IUPAC names for
(a) The seven isomeric aldehydes and ketones with the molecular formula of C5H10O
(b) Aldehydes and ketones with molecular formula of C8H8O containing a benzene ring

ANS:
(a) Seven isomeric aldehydes and ketones with the molecular formula of C5H10O
CH3CH2CH2CH2CHO pentanal
CH3CH2CH(CH3)CHO 2-methylbutanal
CH3CH(CH3)CH2CHO 3-methylbutanal
CH3C(CH3)2CHO 2,2-dimethylpropanal
CH3CH2CH2COCH3 2-pentanone
CH3CH2COCH2CH3 3-pentanone
CH3CH(CH3)COCH3 3-methyl-2-butanone

(b) Aldehydes and ketones with molecular formula of C8H8O containing a benzene ring.
O
C
CH3
CH2
HC O
H
phenylethanone phenylethanal
O C CH3
O
H CH3
C CH3
H 4-methylbenzaldehyde
O C

2-methylbenzaldehyde 3-methylbenzaldehyde

3. Draw the structural formula for each of the following compound

ANS:
CH3CH2C=O CH3-C-CH3
(a) propanal (d) Acetone
H O
(b) 2-ethyl-3-methylpentanal H (e) Acetaldehyde
CH3C=O
H3C CH2 CH CH C O

CH3 H
CH2CH3

(c) 4-methyl-2-pentanone (f) 4-chloro-2-methyl-3-hexanone

O
O
CH3CH-CH2-C-CH3
CH3CH-CH-C-CH-CH3
CH3 CI CH 3

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CHAPTER 9.0: CARBONYL COMPOUNDS

CHAPTER 9.0 : CARBONYL COMPOUNDS UNIT 9.3 : PREPARATION

UNIT 9.4 : CHEMICAL PROPERTIES
LEARNING OUTCOMES:
9.3: PREPARATION OF CARBONYL COMPOUNDS
a) Explain the preparation of carbonyl compounds through:
i. ozonolysis of alkene
ii. Friedel-Crafts acylation to produce aromatis ketone
iii. oxidation of alcohol.
9.4: CHEMICAL PROPERTIES OF CARBONYL COMPOUNDS
a) Explain the chemical properties with reference to:
i. nucleophilic addition with KCN/H+ or NaCN/H+, water, alcohol, sodium bisulphite,NaHSO3 and Grignard reagent
ii. reduction to alcohol using LiAlH4 followed by H3O+ or NaBH4 in methanol or H2/catalyst
iii. condensation with ammonia derivatives such as hydroxylamine, hydrazine, phenylhydrazine and 2,4-dinitrophenylhydrazine (2,4-
DNPH) as identification test for carbonyl compounds
iv. oxidation with KMnO4/H+ or Cr2O72-/H+
v. iodoform test to identify methyl carbonyl group
b) Predict the products formed by reactions of carbonyl compounds with reagents in (a) I, ii, iii, iv and v.
c) Explain the identification tests for aldehyde and ketone using:
i. 2,4-dinitrophenylhydrazine (2,4-DNPH)
ii. Tollen’s, Fehling’s, Benedict’s and Schiff’s reagents
d) Differentiate between:
i. carbonyl and other compounds
ii. aldehydes and ketone
e) Outline the synthesis of compounds related to reactions of carbonyl compounds.

TUTORIAL QUESTIONS :

1. Show how propanal can be synthesised from

(a) 1-propanol (b) 3-hexene

ANS:
PCC
(a) CH3CH2CH2OH CH3CH2CHO
CH2Cl2
(i) O3
(b) CH3CH2CH=CHCH2CH3 2CH3CH2CHO
(ii) Zn/H2O

2. Draw structural formula for the products formed when propanal reacts with
(a) NaBH4 in methanol
(b) C6H5MgBr followed by hydrolysis
(c) LiAlH4 followed by hydrolysis
(d) hot, acidified KMnO4 solution

ANS:

(a) propanal react with NaBH4 in methanol

NaBH4, CH3OH

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CHAPTER 9.0: CARBONYL COMPOUNDS
(b) propanal react with C6H5MgBr followed by hydrolysis

(c) propanal react with LiAlH4 followed by hydrolysis

(d) propanal react with hot, acidified KMnO4 solution

O O
+
KMno4, H , heat
H3C CH2 CH H3C CH2 C OH

3. Show how the following conversions can be carried out:

(a) propanone to propene
(b) cyclohexanone to cyclohexane-1,2-diol
(c) 3-pentanone to 3-chloropentane

ANS:
(a) propanone to propene

(b) cyclohexanone to cyclohexane-1,2-diol

(c) 3-pentanone to 3-chloropentane

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CHAPTER 9.0: CARBONYL COMPOUNDS
4. Complete the following reactions:
(a) i. LiAlH 4
HO CH2 CH2 CH2 CHO + A
ii. H 3O
(b) +
CN
KCN/H
B C OH
CH3
(c) -
O
C
CH3 CH2 CH2 CH2 C O CH3 CH2 CH2 CH2 C O + Ag(s)
H silver mirror

(d) CH3 CH3 H

D
CH3 C CH2 CH2 OH CH3 C CH2 C O
OH OH
(e) O
C2H5COCl
E C C2H5
AlCl3

(f) O +
K2Cr2O7, H
CH3 CH2 CH2 C H F

(g)
O + H2N NH NO2 G

O2N
(h) O
i. CH3CH2MgBr
CH3 C CH3 + H
ii. H 2O, H
ANS:

A: B: O

H H CCH3
HO C CH2 CH2 C OH

H H

C: Ag(NH3)2+OH- D: PCC/CH2Cl2

E: F: CH3CH2CH2COOH

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CHAPTER 9.0: CARBONYL COMPOUNDS
G: H:

CH3
N NH NO2
H3C CH2 C OH

O2N CH3

5. There are many similarities in the reactions of aldehydes and ketones with a wide variety
….of reagents. However, they can be readily distinguished by the way they react with
….oxidising agents. Suggest a chemical test to distinguish them.

ANS:

Fehling solution:- differentiate aliphatic aldehyde from aromatic aldehyde and ketone
O O
-
OH
RC-H + 2Cu2+ complex RC-O- + Cu2O

Fehling solution (blue) copper(I) oxide (red precipitate)

Observation: Blue colour solution decolourise and brick red precipitate form.

O
-
OH
R'C-R" + 2Cu2+ complex No observable change

Fehling solution (blue)

Observation: Blue colour solution remain unchanged.

Tollen Reagent:- differentiate aldehyde from ketone

O O
R C H + 2[Ag(NH3)2] +
+ OH -
2Ag + R C O
-

(silver mirror)
Observation: Silver mirror formed/ Grey precipitate formed
O
R C R + 2[Ag(NH3)2]+ + OH- No observable change
Observation: NO Silver mirror formed/ Grey precipitate formed.

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CHAPTER 9.0: CARBONYL COMPOUNDS
6. Give a chemical test to distinguish between:
(a) benzaldehyde from benzyl alcohol
(b) hexanal from 2-hexanone
(c) 2-pentanone from 3-pentanone

ANS:
(a) benzaldehyde from benzyl alcohol

Tollen’s Test:
Using Ag(NH3)2+OH- : positive test with benzaldehyde (silver mirror is formed)
O O
-
C H C O

Ag(NH3)2+OH-
+ 2Ag

benzaldehdye (silver mirror)

* alternative
Observation: Silver mirror formed/ grey precipitate formed test : can use
HOH2C
2,4-dinitrophenylhydrazine

Ag(NH3)2+OH-
no observable change

benzyl alcohol
Observation: NO silver mirror formed/ grey precipitate formed

(b) hexanal from 2-hexanone

Tollen’s Test:
Using Ag(NH3)2+OH- : positive test with hexanal
(silver mirror is formed)

+ - -
CH3CH2CH2CH2CH2CHO + Ag(NH3)2 + OH CH3CH2CH2CH2CH2COO + Ag
Silver mirror
Observation: Silver mirror formed/ grey precipitate formed
+ -
CH3CH2CH2CH2COCH3 + Ag(NH3)2 + OH No observable change
Observation: NO silver mirror formed/ grey precipitate formed

Or Fehling’s Test

(c) 2-pentanone from 3-pentanone

Iodoform Test:
Using I2 / NaOH : positive test with 2-pentanone
CH3CH2CH2COCH3 I2/ NaOH CHI3 + CH3CH2COO-Na+

Yellow ppt

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CHAPTER 9.0: CARBONYL COMPOUNDS
Observation: Yellow precipitate form.

CH3CH2COCH2CH3 I2/ NaOH No observable change

Observation: Yellow precipitate form.

7. Compound X has the molecular formula of C5H10O. It does not react with Fehling’s
solution but can be reduced to an alcohol with LiAlH 4. Draw all the possible structural
formula of X.

ANS:
X is a ketone; CH3COCH2CH2CH3 , CH3CH2COCH2CH3 , CH3COCH(CH3)2

8. Compounds W and X have the molecular formula of C8H8O. W reacts with hot Fehling’s
solution producing a red precipitate. X gives negative result towards Fehling’s test but it
reacts with LiAlH4 followed by hydrolysis to form alcohol Y. Both X and Y react with
iodine in NaOH solution to yield a yellow precipitate.
Determine the structural formulae of W, X and Y.
Give the products of the reactions between W and LiAlH4/H+, and acidified potassium
dichromate solution respectively.

ANS:
Reaction W(C8H8O) Q(C8H8O) Y(alcohol)
Results Analysis Results Analysis Results Analysis
Cu2+/ hot Red Carbonyl is No Compound is - -
precipitate aldehyde change not aldehyde
LiAlH4 10 alcohol Carbonyl is Alcohol Y Compound is - -
aldehyde carbonyl
compound. It
does not react
with Fehling
solution.
Therefore
compound is
ketone
I2/NaOH - - Positive Contain Positive Contain
methyl methyl
carbonyl alcohol
group group
Conclusions Compound is aldehyde Compound is ketone Compound is 2o
alcohol
O
CH2CHO
OH
CCH3
CHCH3

X Y

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CHAPTER 9.0: CARBONYL COMPOUNDS

CH2CHO CH2COOH CH2CHO CH2CH2OH

+
K2Cr2O7 / H i) LiAlH4

 ii) H3O+
W W

9. Complete the following reaction scheme and write the structural formulae of A to E.
Specify the reagents I to III.
E

conc. H2SO 4

I
CH3 CH2 CH2 OH CH3 CH2 CH2 Br

[O]
O
LiAlH 4 i. CH 3CH2MgBr II
A CH3 CH2 CHO + B CH3 CH2 C CH2 CH3
ii. H 2O, H

III KMnO4, H+, heat

CH3OH, conc. H2SO 4

CH3 CH2 CH2 Cl C D


ANS:

I: PBr3 or PBr5

II: KMnO4/H+,  or K2Cr2O7/H+, 

III: PCl3 or PCI5 or SOCl2

A: CH3CH2CH2OH B:
H3C CH2 HC CH2 CH3

OH

C: D:
O O

H3C CH2 C OH H3C CH2 C OCH3

E: CH3CH=CH2

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CHAPTER 9.0: CARBONYL COMPOUNDS
10. Propanone can be converted to various compounds as shown in the following reactions
scheme.

i. CH3CH2MgBr O KCN/H+ H3O+

C A B
+ CH3 C CH3
ii. H3O

conc. H2SO4,  i. LiAlH 4

+
ii. H 3O
D E
(major product)
(a) Draw the structural formulae of A, B, C, D and E.
(b) What is the rule used to predict the structure of D?
(c) One of the chemical tests that can distinguish D from E is by using Br2 in CH2Cl2.
State the observation and write the chemical equation.
(d) State the type of reaction involved in the formation of E.

ANS:
a) Draw the structural formulae of A, B, C, D and E.
A: B: C:
OH OH OH

H3C C CN H3C C COOH H3C C CH2CH3

CH3 CH3 CH3

D: E:
H3C C CHCH3 OH

CH3 H3C C CH3

(b) Saytzeff‘s rule

(c) One of the chemical tests that can distinguish D from E is by using Br2 in CH2Cl2.
State the observation and write the chemical equation.
CH3 CH3
CH2Cl2
H3C C CH CH3 + Br2 H3C C CH CH3
(D) Br Br

Observation: Reddish brown colour of bromine decolourised.

OH
CH2Cl2
H3C CH CH3 + Br2 no observable change
(E)

Observation: no change on the reddish brown colour of bromine.

(d) Reduction
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CHAPTER 9.0: CARBONYL COMPOUNDS
OBJECTIVE QUESTION

1. Acrolein has the following structural formula:

H2C CH CH
O
Which of the following is not true with regards to acrolein?
A. It does not exhibit stereoisomerism.
B. All the bond angles in the molecule are approximately 90.
C. It undergoes electrophilic and nucleophilic addition reactions.
D. It decolourises aqueous bromine and acidified potassium dichromate solution.

Explanation :
All bond angles in the molecule are approximately 120o.

2. Choose the suitable Grignard reagent that can be used to prepare 2-methyl-3-pentanol from
propanal.
A. (CH3)3CMgBr B. CH3CH2MgBr
C. (CH3)2CHMgBr D. CH3CH2CH2MgBr

3 Butanal can be distinguished from butanone by using the following reagents

EXCEPT
A. Schiff’s reagent B. Tollens’ reagent
C. Iodoform test D. Bromine water

Explanation :
Bromine water is the test for the presence of carbon-carbon double bonds-alkene

4. Which of the following would attack the carbon atom in the carbonyl group?
A. Nucleophile B. Electrophile
C. Free radical D. Carbocation

Explanation:
Since the carbon atom in the carbonyl group is positively polarized, it would be attacked by
negatively polarized atom or group which is nucleophile

5. A compound P reacts with

 sodium hydroxide solution
 2,4-dinitrophenylhydrazine
 phosphorus(III) chloride
P could be
A.
HO COCH3

B.
OCOCH3

C.
HOOC CH3

D. ***
HO C CH2 OH
O

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CHAPTER 9.0: CARBONYL COMPOUNDS
Explanation:
 Only compound that contains aromatic alcohol will react with sodium hydroxide
 Only compound that contains carbonyl group will react with 2,4-dinitrophenylhydrazine
 Only compound that contains aliphatic alcohol will react with phosphorus(III) chloride

6. 2-Hexanone and hexanal can be distinguished by

A. Brady’s reagent
B. Tollens’ reagent
C. Concentrated HCl/ZnCl2
D. Bromine water

Explanation:
TEST REAGENT FUNCTION OBSERVATION
Brady’s Test To test the Produces a
H2N NH NO 2 presence of the yellow/orange
carbonyl precipitate with all
functional group carbonyl
O 2N
compounds

2,4-dinitrophenylhydrazine

Tollens’ Test [Ag(NH3)2]+ To differentiate Aldehyde:

silver amine complex ion aldehydes from Formation of
ketones metallic silver or
grey precipitate
Ketone:
Do not react with
Tollens’ reagent.
Iodoform I2/NaOH To test the Light yellow
Test a solution of iodine in presence of the precipitate will
alkaline medium methyl carbonyl formed
group

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7. Compound Y gives an orange precipitate with 2,4-dinitrophenylhydrazine and shows a

positive iodoform test.

Y could be
A. Ethanal
B. Butanal
C. 2-Propanol
D. 3-pentanone

Explanation:
Compound Y contains carbonyl group and methyl carbonyl group

O O OH

H3C C H H3C C CH3 H3C CH CH3

Ethanal propanone 2-propanol

Methyl Carbonyl
carbonyl group
group

8. Which of the following alcohols can be oxidised to 2-methyl-3-pentanone?

A. CH3CH2CH(OH)CH3
B. CH3CH(OH)CH2CH2CH3
C. (CH3)3CCH(OH)CH3
D. (CH3)2CHCH(OH)CH2CH3

9. The following reaction scheme shows how propene can be prepared from propanal in two
stages using reagents X and Y. Which of the following are the reagents X and Y?
X Y
CH3CH2CHO → CH3CH2CH2OH → H3CH=CH2

A. X: LiAlH4 ; Y: KOH, ethanol, reflux

B. X: NaBH4 ; Y: conc.H2SO4, heat
C. X: dillute H2SO4 ; Y: conc.ethanol, reflux
D. X: dillute H2SO4 ; Y: KOH, ethanol, reflux

10. When aldehyde is heated with Fehling's solution, it gives a precipitate of

A. Cu2O
B. CuO
C. Cu2O & CuO
D. C

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