Here is an post-mortem analysis / "how
to" for the Final. The questions
are split by the sections. At the start of each section are a few
suggestions
of what to look for or how to tackle the question type.
Qu1: D
The reaction is a nucleophile adding to a carbonyl of an ester i,
aldehyde
ii and ketone iii. The electronic effect of the group attached to
the C=O controls the electrophilicity of the C=O. In order of the
groups electron donating ability CH3O- > CH3-
> H-
so the ester is the least electrophilic and the aldehyde the most
electrophilic.....so we get the reactivity order of ii> i > iii.
Qu2: AB
The reaction is electrophilic aromatic substitution, and we need to
look at the substituent effects on the aromatic ring. -NO2
is a deactivating group due to electron withdrawal by resonance and
inductive
effects, -Cl is slightly deactivating due to electronegativity and the
N atom of an amide slightly activating due to the possibility of
electron
donation by resonance. So iii > ii > i.
Qu3: A
Look at where the H is attached and think of the factors that stabilise
charge such as electronegativity, resonance, inductive effects etc. i
gives
an O -ve that is further resonance stabilised to give a second O -ve (a
carboxylic acid), both ii and iii give C -ve. In ii we have an
active
methylene where the -ve charge can be resonance stabilised onto 2
possible C=O creating O -ve. iii is a terminal acetylene but still a C-
is formed. FYI : pKa values.... acid about 5, diketone about 9 and an
acetylene
about 25. So in terms of acidity i > ii > iii.
Qu4: A
A set of similar organometallic reagents.... reactivity correlates
to reactivity of the metal, so Li > Mg > Cu.... therefore i >
ii > iii.
Qu5: A
Nucleophiles are electron donors so we have to look at factors that
affect electron availability. Compare i and ii, they only differ in the
nature of the charged atom O vs S. Nucleophilicity increase down
a group due to polarisability factors so i > ii. ii and iii
are both
O systems. The phenoxide iii has some resonance stabilisation of the
charge
making it less nucleophilic than the simple alkoxide, So overall we
have
i > ii > iii.
Qu6: A
Benzene, i, has the highest resonance energy per C=C of any system
at about 36 kcal/mol. Pyridine ii has slightly less at about 28
kcal/mol
and furan iii is a lot lower around 16kcal/mol (more diene
character).
So we have i > ii > iii.
Qu7: D
Compare O and S systems first (same group). Acidity increases
down a group (e.g. HI > HBr > HCl >HF) due to size effects (i)
length and
strength of HX bond and (ii) the ability of the larger atom to accept
the
charge, so RSH > ROH (acidity) therefore RO- > RS- in terms of
basicity.
Note electronegativity should not be used when comparing atoms in
different
rows of the periodic table. Now compare O and C systems (same
row).
O is more electronegative than C so is less willing to share electrons
and therefore it is less basic... so C- > O- (basicity). Overall
then we
have C- > O- > S- or ii > iii > i.
Qu8: C
Electrophilic addition to CC pi bonds in alkenes and alkynes with
sulphuric
acid. Reaction is controlled by the stability of the intermediate
carbocations.
System i gives a secondary cation, ii gives a secondary cation where
the
lone pairs on the adjacent O can give some resonance stabilisation and
iii gives less favourable vinyl cation. Most stable cation is the
easiest
to form, so ii > i > iii.
Qu9: A
The reaction is electrophilic aromatic substitution, and we need to
look at the directing effect of the groups. i and ii both have alkyl
groups
=> a electron donating group => ortho/para director whereas iii
is a C=O
of a ketone => a electron withdrawing group => meta
director Steric
effects will block the ortho site more with the larger R group in i
that
ii , so yield of para i > ii > ii.
Qu10: C
Comparing i and ii we have an isolated and a conjugated diene, so the
conjugated diene, ii, is more stable. The cyclobutadiene in iii is also
a conjugated system, but it is antiaromatic and quite destabilised.
Overall
then we have ii > i > iii.
A = IR gives C=O, H-NMR gives -OCH3
at 4ppm and a
monosubstituted aromatic at 7-8ppm... it's an ester, methyl benzoate,
B = IR gives an alcohol, H-NMR gives a monosubstituted aromatic
at 7-8ppm, a CH2 and the -OH so we have benzyl alcohol
C = IR gives an alcohol, H-NMR gives a disubstituted aromatic,
a CH3 and the -OH so we have a phenol, p-methylphenol
D = IR gives C=O, H-NMR gives an aldehyde at 10ppm, and
a monosubstituted aromatic at 7-8ppm... its an aromatic aldehyde,
benzaldehyde
E = IR gives no C=O, H-NMR gives a monosubstituted aromatic
at 7-8ppm and alkene at 5-7ppm : phenylethene
AB = IR gives C=O, H-NMR gives a monosubstituted aromatic at
7-8ppm and a CH3 at 2.5ppm (next to a C=O ?) its an aromatic
ketone, acetophenone
Qu11: B
Lucas test is for alcohols but not phenols.
Qu12: AB
DNP implies an aldehyde or ketone, the chromate tells us it is not
oxidisable, so it must be the ketone.
Qu13: C
Ferric chloride test is for phenols.
Qu14: B
DNP implies it is not an aldehyde or ketone (no precipitate) and the
chromate tells us it is is oxidisable, so it must be an oxidisable
alcohol
(and therefore not a phenol).
Qu15: AB
The yellow precipitate due to the formation of iodoform, CHI3,
in the iodoform test indicate the presence of a methyl ketone.
Qu16: E
Tests for the presence of C=C in alkenes (and alkynes).... this system
is an alkene.
Qu17: D
DNP implies an aldehyde or ketone, but the iodoform says it is not
a methyl ketone, so must be the aldehyde.
Qu18: A
DNP implies it is NOT an aldehyde or ketone, therefore, given the C=O
system is required, from the options it must be the ester.
Qu19: AB
The heterocycles (i.e. systems with non-C atoms in rings) are
E, AB, AC, AE and BC.... but only E, AB and AE contain nitrogen. The N
atoms in E aren't basic (no lone pairs to donate). In AE the lone
pair on N is part of the aromatic system so it is not readily donated
and
therefore the N is not very basic. In contrast in AB, the lone pair is
NOT part of the aromatic system (there are already 6 p
electrons from the 3 p bonds) so it is quite
basic.
Qu20: A
If n=2, then we need a 10 p system.....
only A has 10 p electrons.
Qu21: AD
4n p electron systems are B, C and AD. B
is non-aromatic because it is not a cyclic conjugated p
system.
C will turn out to be the answer to qu 25. AD is an 8 p
system, it is cyclic and conjugated.... if planar it would be
anti-aromatic
and therefore destabilised. In order to avoid this destabilisation, the
ring twists out of planarity and so is "non-aromatic".
Qu22: A or AB or AC
Aromatic as drawn means we are considering A, E, AB, AC, AE and BC.
Now we are looking for a basic system that also has an aromatic
conjugate
acid, so the lone pair used in the acid/base reaction cannot be part of
the initial aromatic unit. Protonation of E, AE and BC will
give non-aromatic conjugate acids
Qu23: B
Non-aromatic as drawn means we are considering B, C and D. Now
we are looking for a system that becomes aromatic when a proton is
removed.
B is a 4 pelectron system, so the extra lone
pair formed when H+ is removed from the -CH2- makes an aromatic 6 p
electron
system. C and D are discussed in Qu24 and 25 below.
Qu24: D
Non-aromatic as drawn means we are considering B, C and D. The
example of tautomerism we met was enol / ketone (during addition of
water
to
alkynes). If we look at D and convert each of the H-C-C=O to C=C-OH
we get a tri-enol, 1,3,5-trihydroxybenzene, which is aromatic.
Qu25: C
Non-aromatic as drawn means we are considering B, C and D. In
either B or D resonance cannot alter the CH2 units to become part of
C=C
and so allow a cyclic conjugated system to form. In C if we make
the C=C become -C-C+ this gives a 6p electron
system in the five membered ring and a 2p electron
system in the three membered ring, both of which are aromatic.
Qu26: D
Esters react with 2 equivalents of Grignards to give tertiary alcohols
after work up so in this case we will get a diol since we have a cyclic
ester to start with. Excess PBr3 will convert the alcohols
to
bromides which are then eliminated giving a diene. Counting C
atoms
: SM = 5 plus 2 from 2 eq. methyl magnesium bromide = 7 C.
Qu27: C
Amines react with acid chlorides to form amides. Friedel-Crafts
alkylation
of the aromatic ring will be para- . The alkyl group is then oxidised
to
an acid -CO2H and finally the amide is hydrolysed back to
the
amine. So we are looking for p-aminobenzoic acid, C.
Qu28: C
The acid reacts with thionyl chloride to form the acid chloride which
in turn reacts with the amine to form the amide. Reduction of the amide
gives an amine so must be B or C. It maybe useful to count C atoms....
remember the C from the original carbonyl will now be in the amine.
Qu29: B
The peracid will react with the C=C to form an epoxide. The amide ion
is a good nucleophile and will attack the epoxide from the least
hindered
end giving the 2-amino-3-alcohol product, B.
Qu30: D
Diels-Alder reaction followed by reduction of the ketone to a secondary
alcohol but no reduction of the C=C. Count C atoms.....
Qu31: B
Diazotise the amine, then convert it to the nitrile, which is then
hydrolysed to the acid.... so we are looking for m-hydroxybenzoic acid,
B.
Qu32: C.
Protect the more reactive ketone as a cyclic ketal. React the ester
with 2 equivalents of the Grignard reagent, work-up then removal of the
ketal protecting group reforms the ketone.... hence we have a tertiary
alcohol / ketone system, C.
Qu33: B
The cyclopropane is formed by the Simmons-Smith reaction of the Zn
system with an alkene, which has in turn been made by a Wittig reaction
(note the P species) from cyclohexanone, B.
Qu34: E
The ketone has been formed by the oxidation of a secondary
alcohol.
The secondary alcohol must have been formed by the reaction of a
Grignard
reagent (E) with the methanoate ester.
Qu35: D
The alkyl group has been added to the benzene via an acylation then
a Wolff-Kischner reduction. We are looking at the preparation of the
acyl
chloride for the acylation, so we need the C4 acid, D.
Qu36: C
The sequence looks like an aldol (note the enone product) preceded
by an ozonolysis with a reductive work-up. The product is C6, so
the original cycloalkene is also C6. The required intermediate
dicarbonyl
can be visualised by "breaking" the product at the C=C, where the C=O
would
have been on the beta-C of the C=C. Hence we have an aldehyde there
with
a methyl ketone at the other end of the chain. A gives a
dialdehyde
on ozonolysis, B is C7, C is good, D and E don't react with ozone as
they
lack C=C.
Qu37: E
Sequence involves the methylation of a ketone enolate, where the ketone
has been formed by the PCC oxidation of a secondary alcohol itself
formed
by the hydroboration of an alkene (anti-Markovnikov). Working with the
product, remove one methyl group, convert the C=O to C-OH then to the
trisubstituted
alkene reveals E.
Qu38: E
Tough one despite its apparent simplicity. The only material with the
correct oxidation state is E. Reaction involves loss of water followed
by a carbocation rearrangement. A, B and C would give alcohols
via
hydration reactions. D would react to via a rearrangement to also give
an alcohol, 2,3-dimethyl-2-butanol.
Qu39: C
The sequence looks like an intramolecular Claisen (i.e. a
Dieckmann)
condensation achieved via the esterification of a dicarboxylic acid
from
an ozonolysis with an oxidative work-up. The product is C6, so
the
original cycloalkene is also C6. The required intermediate diester can
be recreated by "breaking" the product at the ring C-C between the -OH
and -CH2OH. To get the diacid from the ozonolysis, the
alkene needs C6, symmetrical and only 1,2-disubstituted... so it has to
be cyclohexene.
Qu40: C
A Sandmeyer reaction of a diazonium salt to give the bromide : use
CuBr.
Qu41: BC
Convert the Br to a carboxylic acid with one new C atom. This suggests
using a Grignard reagent and carbon dioxide.
Qu 42: D
Acid to acid chloride, an acid derivative..... need to use thionyl
chloride. The triethyl amine is used to react with the HCl by-product.
Qu43: AB
Not easy to spot, but this is a Friedel-Crafts reaction on benzene.
Qu44: B
Convert the -CH3 to a -CH2Br. Since this
is a reaction that converts a simple C-H to a C-Br, need radical
substitution.
Qu 45: AD
Bromide to a nitrile... looks like a nucleophile substitution of a
benzylic halide using a cyanide as the nucleophile.
Qu46: CD
Need to add an ester group next to the nitrile which is an
electronwithdrawing
group.... this means we could use a strong base to form an enolate then
add an acylating agent.
Qu47: ABC
Now need to add a methyl group next to a nitrile and an ester, both
of which are electronwithdrawing groups. Use a base to form an enolate
then add an alkylating agent.
Qu 48: BE
Another tricky one.... how to get rid of a C group and get a carboxylic
acid ? Decarboxylation ? So hydrolyse both the nitrile and ester to a
dicarboxylic
acid which will then undergo the loss of carbon dioxide.
Qu49: D
Draw the product, you've added -OH and -Cl to an alkene. Hydration
is addition of water, there is no rearrangement. You need to know the
mechanism
by which this reaction occurs.... HOCl is equivalent to HO- and Cl+, so
the chlorine is the electrophile that adds first to the C=C.
Qu50: D
Aromaticity...the stability of the product conjugate base is what makes
the system so acidic for a seemingly simple C-H bond.
Qu51: B
High T suggests thermodynamic conditions when equilibria and hence
reversible reactions are present.
Qu52: B
Need to know the process, the oxidation is really an 1,2-elimination
of a chromate ester... the critical "item" is the presence of the H- at
the carbinol carbon... i.e. we need to have had a H-C-OH unit to start
with.... clearly not possible in a tertiary alcohol where all the
groups
attached to the carbinol C are alkyl groups.