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H2 9647 CHEMISTRY
2014 JC2
Carbonyl Compounds
Tutorial 7
Compulsory Questions
[To be discussed during tutorial. Do all questions on foolscap paper. Show all
relevant workings.]
Fill in the structural formulae of the organic compounds A D, and state the reagents
and conditions for steps I V.
C9H10O3
K2Cr2O7 /H
heat
Tollens
reagent
No silver mirror
2,4-DNPH
Orange ppt
II
IV
III
+ CHI3
Tollens
reagent
Silver
mirror
Fehlings
solution
No ppt
9647 H2 Chemistry
Page 1 of 25
Step
I
II
III
IV
HCl(aq), heat
9647 H2 Chemistry
Page 2 of 25
2(a)
Name and describe the mechanism of the reaction between ethanal and
hydrogen cyanide, stating and explaining the use of any other reagents
required for the reaction. Show clearly the structural formulae of any
intermediates, as well as of the products.
Mechanism: nucleophilic addition
Other reagent required: Trace amount of NaOH
Step 1 :
O -
O:
slow
C +
H
:CN
CH3
CH
CN
Step 2 :
O:
CH3 C
CN
CN
OH
CH3 C
CN
:CN
H+
:CN -- (1)
The trace NaOH will neutralise the H+, causing [H+] to decrease.
9647 H2 Chemistry
Page 3 of 25
(ii)
H
O
H
N
(iii)
O-
O:CN-
C
R'
Attack from the bottom
9647 H2 Chemistry
(50%)
and
CN
C
NC
R'
R
(50%)
Page 4 of 25
Starting from a suitable carbonyl compound of your choice, and using a cyanohydrin
as an intermediate, devise a 3-stage synthesis of compound C
.
CH3C(OH)(CH3)CO2CH2CH3
C
Suggest reagents and conditions for each step, and draw the structural formula of
every intermediate compound.
CH3 O
C O
CH3
C O CH2CH3
OH
Analysis:
CH3 O
CH3
CH3
C O CH2CH3
CH3
OH
C COOH
HO CH2CH3
OH
=
Acid
can be formed from a cyanohydrin
Alcohol
C CN
OH
CH3
CH3
C COOH
OH
9647 H2 Chemistry
CH3
Dilute HCl
CH3
heat
HCN in aqNaOH
CH3
C CN
OH
C CH3
O
10-20C
Page 5 of 25
N10/II/4
4
Most of the chemistry of magnesium relates to its ionic compounds. However,
magnesium does form an important group of covalent compounds which are known as
Grignard reagents.
In 1911, the French chemist F.A.V. Grignard reacted small pieces of magnesium with a
warm solution of bromoethane in a dry, non-polar solvent and obtained a solution
containing ethylmagnesium bromide, C2H5MgBr. Many Grignard reagents, with
different alkly and aryl groups, have now been prepared and are widely used in organic
syntheses.
A typical example of the use of a Grignard reagent is the two-step reaction of
C2H5MgBr with propanone as shown below.
OMgBr
C2H5MgBr + CH3COCH3
(a)
CH3
C CH3
OH
CH3
C 2H 5
C CH3
+ MgBrOH
C 2H 5
MgBr
(b)
is
OH
CH3
(c)
C H
CH3CH2CH2MgBr + CO2
9647 H2 Chemistry
Page 6 of 25
OMgBr
OH
C O
C O
CH3CH2CH2
CH3CH2CH2
J97/I/17 (modified)
5
Three compounds E, F and G all have the molecular formula C3H6O. E is an alcohol, F
is a ketone, and G is an aldehyde.
(i) Draw possible structural formulae for E, F, and G.
CH2=CHCH2OH or CH3CH=CHOH
CH3
CH3
G
(ii)
C CH3
CH2
C H
O
Describe tests (reagents, conditions and observations with each compound) that
would allow you to show that:
1. E is an alcohol, whereas F and G are not.
2. F and G are carbonyl compounds, whereas E is not.
3. G is an aldehyde, whereas E and F are not.
Write balanced equations for all reactions that occur.
H2C CHCH2OH +
9647 H2 Chemistry
PCl5
Page 7 of 25
CH3
CH2
NO2
+ H2N NH
H3C C N NH
O2N
C H + H2N NH
O
NO2 + H2O
O2N
NO2
CH3
CH 2
NO2 + H 2O
C N NH
H
O2N
O2N
CH3
CH2
C H
O
2[Ag(NH3)2]+ + 2OH-
CH3
CH2
C O-NH4+ + 2Ag
O
+ H2O +
9647 H2 Chemistry
3NH3
Page 8 of 25
oxidation
PCl5
J
N
dehydration
HCl
O
(a)
What structural feature must be present in K for it to give a positive test with alkaline
aqueous iodine in forming L and M? Hence, state the class of compound K belongs
to.
J undergoes oxidation to give K
K could be a ketone
[1]
(b)
C CH3
K must contain
structure. [1]
Deduce the identity and structural formula for each of the compounds J to O.
J burns with a smoky flame and has comparable C and H atoms with no of C
atoms 6.
OH
H
J is
K is
C CH3
OH
[1]
9647 H2 Chemistry
C CH3
[1]
Page 9 of 25
C OL is
and M is
O
[1]
CHI3
[1]
N is
C CH3
Cl
[1]
H H
O is
C C H
[1]
(c)
State the reagents and conditions necessary to make the following conversions:
(i)
J to K
(ii)
J to O
(i)
J to K
Reagents : K2Cr2O7 in dilute H2SO4 [1]
Conditions : reflux
(ii) J to O
Reagents : concentrated H2SO4
Conditions : heat at 170C
9647 H2 Chemistry
[1]
Page 10 of 25
[Deductive Question]
A certain industrial cleaner and paint solvent was distilled to produce a single
compound D. When D reacted with 2,4-dinitrophenylhydrazine, an orange precipitate
was produced. With alkaline aqueous iodine, D gave a pale yellow precipitate. D did
not react either with warm acidified potassium dichromate (VI) or with aqueous
bromine. Reduction of D with hydrogen over a catalyst produced equimolar mixture of
two isomers, E and F, with the molecular formula C4H10O.
Suggest structural formula for D, E and F and explain the reactions involved.
O
CH3
structure
OH
CH3
D cannot have
9647 H2 Chemistry
Page 11 of 25
C structure.
OH
E and F
Both E and F contain a chiral carbon hence they are optical isomers. A
OH
CH3
OH
C
H
D is
CH2CH3
CH3CH2
H
CH3
O
CH3
9647 H2 Chemistry
CH2 CH3
Page 12 of 25
[Chemical Tests]
Three different compounds of molecular formula C8H8O give precipitates with
2,4-dinitrophenylhydrazine and can be reduced by lithium aluminium hydride in dry
ether to compounds of molecular formula C8H10O.
Suggest structures for these three compounds and explain how they could be
distinguished from one another by means of chemical tests.
[The isomerism does not arise from a difference in the orientation of substituents in
the benzene ring.]
All three compounds contain comparable no of C and H atoms with no of C atom 6.
All contain benzene ring.
All three compounds undergo condensation with 2,4-DNPH to form orange ppt.
All three are carbonyl compounds
All three compounds undergo reduction with LiAlH4 to form alcohols.
3 possible structures (C8H8O) :
H O
C CH3
C C H
O
CH3
C H
H
A (aromatic ketone)
B (aliphatic aldehyde)
NOT AROMATIC!!
C (aromatic aldehyde)
9647 H2 Chemistry
Page 13 of 25
N07/P3/Q3(d)
9
In 1834 the French chemist Eugene Peligot published his investigations into the action
of heat on the Group II salts of carboxylic acids. He discovered that the salts
decomposed to give the metal carbonate and a carbonyl compound. This calcium
ethanoate produces propanone.
(CH3CO2)2Ca
CaCO3 + (CH3)2CO
When this reaction is carried out by heating a 1:1 molar mixture of calcium ethanoate
and calcium methanoate, (HCO2)2Ca, a mixture of three carbonyl compounds is
formed, all having Mr < 60.
(a)
Suggest the structures of the three carbonyl compounds, and the ratio in which they
might be produced.
O
CH3
C CH3
O
H C CH3
O
H C
(b)
Suggest two chemical tests that could be used to distinguish the three carbonyl
compounds from each other. You should state what you would observe for each
compound in each test.
(i)
Add Tollens / Fehlings Reagent to the 3 compound in separate test tubes and
warm. A silver mirror is formed in the test tubes of methanal and ethanal, while no
silver mirror seen in the test tube containing propanone.
(ii)
Add aqueous iodine with sodium hydroxide to the 2 compounds in separate test
tubes and warm. The brown iodine decolourised and a pale yellow precipitate
appears in the test tubes containing ethanal while the test tube containing methanal
remains brown with no yellow precipitate being formed.
Alternative answer:
(i) Aq. Iodine with sodium hydroxide, warm
(ii) Tollens / Fehlings Reagent
9647 H2 Chemistry
Page 14 of 25
10
[Planning]
A student was given 4 unlabelled bottles and each bottle contains one of the
following organic compounds: cyclohexene, butan-1-ol, benzaldehyde, propanone.
Outline a sequence of simple chemical tests by which the studen could identify each
of the above organic substances. The student is not allowed to identify the
substances by elimination.
Test
Procedure
Observation
Decolourisation of
reddish-brown
solution is seen
for the test tube
containing
cyclohexene.
Chemistry Involved
No
decolourisation
of reddish-brown
solution is seen
in the other test
tubes.
2
White fumes of
HCl produced,
which turn damp
blue litmus paper
red is seen for the
test tube containing
butanol
No white fumes
are seen in the
other test tubes.
9647 H2 Chemistry
Silver mirror is
observed in the
test
tube
that
contains
benzaldehyde.
Benzaldehyde
undergoes oxidation
reaction Tollens
reagent to give a silver
mirror.
No silver mirror
is observed in the
Page 15 of 25
Orange ppt of
hydrazone is
formed for the test
tube containing
propanone.
Propanone undergoes
condensation with 2,4dinitrophenylhydrazine
Alternative test:
Place 1 cm3 of each of the
other organic compounds in a
test tube.
Add 1 cm3 of I2 (aq) and 1 cm3
of NaOH aqueous. Warm the
mixture
Decolourisation
of brown iodine
solution.
Pale
yellow ppt of CHI3
is formed for the
test tube containing
propanone.
THE END
9647 H2 Chemistry
Page 16 of 25
Name:
Date:
Class:
Score:
/20
Write an expression for the acid dissociation constant, Ka, for the weak acid
hydrocyanic acid, HCN.
H+(aq) + CN-(aq)
HCN(aq)
Ka
(ii)
H CN
HCN
[1]
For HCN, Ka = 4.9 x 10-10 mol dm-3. Use this value to calculate [H+] in a
0.100 mol dm-3 solution of HCN, and hence calculate the percentage of HCN
molecules that are ionised.
HCN(aq)
H+(aq) + CN-(aq)
7 106
100% = 0.00700% [1]
0.100
(i) Explain how the addition of solid sodium cyanide, NaCN, will alter the
percentage of HCN molecules ionised.
HCN(aq)
H+(aq) + CN-(aq)
Adding NaCN will increase the concentration of CN- ions in the solution. By Le
Chateliers Principle, the equilibrium position will shift to the left [1] to reduce the
concentration of CN- ions, thus lowering the % ionisation of HCN [1].
(b)
9647 H2 Chemistry
Page 17 of 25
Cyanohydrins are useful intermediates in organic syntheses. They can be made by reacting
ketones with a solution of HCN to which a small amount of NaCN has been added.
(CH3)2CO + HCN
(CH3)2C(OH)CN
In a series of experiments, the reaction was carried out with different concentrations of the
three reagents, and the following relative initial rates were obtained.
Experiment
number
1
2
3
4
[(CH3)2CO] /
mol dm-3
0.040
0.050
0.040
0.050
[HCN] /
mol dm-3
0.040
0.040
0.040
0.050
[NaCN] /
mol dm-3
0.008
0.008
0.006
0.006
(ii) Use these data to deduce the order of reaction with respect to each of the three
reagents showing how you arrive at your answers. Hence write a rate equation
for the reaction.
Let Rate = k[propanone]a[HCN]b[NaCN]c
From Experiment 1 & 2
a
b
c
Rate2 k 0.050 0.040 0.008
1.25
a
Solving, a = 1.
Order of reaction is 1 wrt propanone. [1]
From Experiment 1 & 3
a
b
c
Rate3 k 0.040 0.040 0.006
0.75
a
Solving, c = 1.
Order of reaction is 1 wrt NaCN. [1]
From Experiment 1 & 4
Solving, b = 0.
Order of reaction is 0 wrt HCN. [1]
Rate = k[propanone][NaCN] [1]
9647 H2 Chemistry
Page 18 of 25
(iii) Describe a mechanism that is consistent with your rate equation, and indicate
which step in the mechanism is the rate determining step. Explain your reasoning.
(CH3)2CO + HCN
Rate = k[propanone][NaCN]
(rate eqn)
Rate equation is not based on the overall stoichiometric chemical equation but on the R.D.S.
of a multiple-step mechanism. [1] Since order of reaction wrt HCN is 0, HCN is not
involved in the slow step. Reaction is non-elementary with the rds involving 1 propanone
molecule and 1 NaCN molecule.
HCN(aq)
Step1:
H+(aq) + CN-(aq)
NaCN Na+ + CN
O-
C CH3 + CN-
CH3
CH3
C CH3
CN
Step2:
OCH3
C CH3 + HCN
OH
CH3
CN
Step3:
[3]
C CH3 + CNCN
(iv) Hence suggest why propanal, CH3CH2CHO, reacts with HCN at a faster rate than
does propanone.
Propanone consists of 2 bulky methyl groups around the carbonyl carbon, creating more
steric hindrance for the attack of the nucleophile.
OR
The 2 electron donating methyl groups dispersed the positive charge on the carbonyl
carbon to a larger extent on propanone than pronanal, making it less susceptible to
nucleophilic attack. [1]
9647 H2 Chemistry
Page 19 of 25
(v) State the roles of HCN and NaCN in the mechanism of this reaction.
HCN is the reactant and NaCN is the catalyst. [1]
(c)
The reaction between propanal and HCN produces an equimolar mixture of two
isomers D and E. When the vapour of either isomer is passed over hot aluminium
oxide, the same mixture of two cyanoalkene isomers F and G is produced.
Describe the types of isomerism shown here.
Explain why each of the two isomers D and E produce that same mixture of
cyanoalkenes.
You should include the displayed formulae of all the compounds D - G in your answer.
Type of isomerism shown in D and E: optical isomerism [1]
H
O
O
C
N C
H
H C H
C N
H C H
H C H
H C H
H
C C
N
C
C C
H
H
H C C H
H H
H C C H
H H
F(cis-isomer)
Both D and E undergoes elimination of H2O from the same adjacent carbon atoms
to give the same product which could exist in two different ways, due to restricted
rotation about the C=C double bond. [1]
END
9647 H2 Chemistry
Page 20 of 25
Carvone, C10H14O, is the main flavoring material in spearmint oil. It reacts with
2,4-dinitrophenylhydrazine to yield an orange precipitate but does not react with
Tollens reagent. When carvone is treated with hydrogen gas in the presence of a
nickel catalyst, it reacts to yield a compound A (see below). Carvone can also
undergo oxidation with acidified KMnO4 under several hours of reflux to form
compound B (see below), carbon dioxide and water.
OH
CH
CH3
CH2
CH
CH
CH2
CH3
CH
CH2
CH3
HO
C
O
CH2
CH
CH2
C O
CH3
CH3
O
CH
CH3
CH2
CH2
CH C
CH
CH2
9647 H2 Chemistry
CH3
Page 21 of 25
08/NJC/III/1(c)
2
R'
R
MgCl +
H2O
OH
Mg(OH)Cl
H
Given the carbon-magnesium bond in Grignard reagent is highly polar,
state the type of reaction between R MgCl and the aldehyde.
(i)
nucleophilic addition
(ii) R-MgCl reacts with propanal to give compound A. Compound A gives a yellow
precipitate with I2 in aqueous NaOH. When compound A reacts with excess
concentrated H2SO4 at 170oC, compounds B and C are formed. Compound B
upon reaction with hot acidified potassium manganate(VII), produces compound
D and effervescence is observed. Compound C exists as a pair of geometric
isomers. Deduce the structure of compounds A - D.
By observing pattern in general eqn given above,
R-MgCl + CH3CH2CHO CH3CH2CH(OH)(R) +Mg(OH)Cl
Compound A
Compound A
H
H3C
CH2CH3
OH
C
CH2CH3
H3C
CH3
C
H
9647 H2 Chemistry
H3C
C
H
C
CH3
Page 22 of 25
C
Compound B is
CH2CH3
HO
O
Compound D is
CH2CH3
Compound C
H3C
CH3
C
H
9647 H2 Chemistry
H3C
C
H
C
CH3
Page 23 of 25
Multiple-Choice Questions
1.
For which one of the following can a solution of iodine in aqueous sodium hydroxide
be used to distinguish between members of the pair?
A. CH3CHO and CH3COCH3
B. CH3CH2CHO and CH3COCH3
C. CH3CH2OH and CH3CH2CH(OH)CH3
D. CH3OH and CH3CH2CHO
2.
Which reagent gives the same visible result with propanal and with propan-2-ol?
A. 2,4-DNPH
B. acidified potassium dichromate (VI)
C. concentrated sulphuric acid
D. Tollens reagent
3.
4.
The product of the reaction between propanone and hydrogen cyanide is hydrolysed
under acidic conditions.
What is the formula of the final product?
A. CH3CH2CH(OH)CO2H
B. CH3CH2CH2CO2H
C. (CH3)2CHCONH2
D. (CH3)2C(OH)CO2H
5.
6.
9647 H2 Chemistry
Page 24 of 25
7.
A
B
C
D
8.
II
elimination
reduction
reduction
elimination
N07/P1/Q23(H1)
9
A compound, X, of molecular formula C5H10O showed the following behavior.
It gave an orange precipitate with 2,4-dinitrophenylhydrazine reagent.
It gave a yellow precipitate when warmed with alkaline aqueous iodine.
It showed no reaction with Fehlings reagent.
Which is the correct formula of X?
H H O H H
H C C C C C H
H H
A.
H H
H H H H
H C C C C C
H
H H H H
B.
H H H
H C C C C C H
H H H O H
C.
H H
H C C
D.
9647 H2 Chemistry
H CH3
H
C C
H
O
H
Page 25 of 25