Here is an post-mortem analysis / "how to" for the MT. 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: A
Carbocation
stability.... due to (i) alkyl groups, which are weak electrons
donors and (ii)
resonance with pi bonds. These effects add stability due to charge
delocalisation. i is
secondary and benzylic. ii is
tertiary and iii is a phenyl
cation (which are very unstable C+). A simple primary benzylic
cation is almost as stable as a tertiary so a secondary benzylic cation
is more stable than a tertiary cation, hence i > ii > iii.
Qu2: AB
The systems are all dienes... diene
stability is such that conjugated are more stable than isolated
which in turn are more stable than cumulated. For individual C=C,
alkene
stability is such that a more highly substituted C=C (i.e. more
alkyl groups on the C=C unit) is more stable. The more stable a system
is, the less exothermic the heat of hydrogenation will be for the
reduction to the alkane. i is
an isolated diene, ii is
conjugated with two disubstituted C=C and iii is conjugated with one
trisubstituted and one disubstituted. Overall then iii > ii
> i.
Qu3: B
If you know your pKa's then this is easy : water = 15.7 terminal alkyne
pKa = 26, t-butanol
= 18. Remember the lower the pKa the stronger the acid, so i >
iii > ii. What if you don't remember your pKas ?
(why
not ?) Then you'll need to deduce it. Think
of the simple acid equation HA <=> H+ A-
then look for factors that stabilise A-..... first compare water and
the alcohol.... if you recall, alkyl groups are weak electron donors
and stabilise cations.... therefore they destabilise anions.... so
water is more acidic than an alcohol. Now what about the alkyne ?
Maybe the easiest way here is to think about the bases that are used in
synthesis to make the acetylide ion.... sodium amide is the common
choice.... that implies that alkoxides, RO-, are probably not strong
enough bases so the alkyne is a weaker acid than the alcohol.
Qu4: A
Resonance
energies measure stability. Benzene i
has a high resonance energy (36 kcal/mol) due to the aromaticity of the
cyclic pi system. Furan ii is
also aromatic but the aromatic stabilisation is less than that of
benzene (16 kcal/mol). The cyclohexadiene in iii is an isolated diene so it has
zero resonance energy (well, there is no resonance !). Therefore
we get i > ii > iii.
Qu5: AB
Reaction is the Diels-Alder
reaction. The normal Diels-Alder is favoured by having electron
withdrawing groups on the dienophile. i
the oxygen substituent here has a lone pair next to the pi
system which can be donated to the pi system by resonance. In ii we have a carbonyl which is an
electron withdrawing group (think of the important contributor where
the C=O is drawn as +C-O- hence the +ve C attracts electrons. In iii there are 2 carbonyl groups
attached to the C=C. Overall then we have iii > ii > i.
Qu6: A
All CC bonds, the thing that is changing is the hybridisation
of the C atoms involved in the bond. Review
? In i both C are sp3, we
have a simple standard sigma bond (1.54 pm) In ii one C is sp3 the other is
sp2. Since the sp2 has greater s character, the orbital is
smaller and the result is a shorter bond (1.51 pm). In iii both C are sp2, hence shorter
again, plus there is the additional bonding interaction due to the
adjacent p orbitals (1.46pm). Overall i > ii > iii.
Qu7: AB
Reaction is the hydrogenation
of either alkene or alkynes.
The reactivity towards reduction is determined by the strength of the
pi bonds so alkynes reduce more rapidly than alkenes. Aromatic C=C
reduce more slowly than alkene C=C due to the aromatic stabilisation.
So iii > ii > i.
Qu8: A
Reaction is the hydroboration
oxidation of an alkene. This gives the
anti-Markovnikov alcohol via a syn addition due to the concerted
addition
of the B and H across the C=C. Since no C+ forms, there is no
carbocation
rearrangement. First draw 2-methyl-1-pentene, then add the -OH
to the least substituted end of the C=C. So i is the major
product
and ii is a minor product
(the Markovnikov product). iii
is only
obtained
is there has been a rearrangement. Overall then i > ii > iii.
Qu9: A
Sucrose is the disaccharide of glucose and fructose, they are the
component monosaccharides.
Qu10: A
It's about making a better leaving group... protonating the oxygen
in the glycosidic bond means there is a neutral leaving group.
Qu11: B
An anomeric carbon is typically attached to two oxygen atoms by single
bonds. In this case there is only one C-O bond there.
Qu12: A
Reactions are second order if the rate law has depends on the
product of the concentrations of two molecules, either different
species A and B or the same species, A with A.
Qu13: A
Alcohols
undergo dehydration, an elimination with strong acid via the E1
pathway.
Qu14: B
The reaction
of alcohols with HCl in the Lucas test is an SN1 type reaction so
the rate depends on the relative stability of the carbocation produced.
Qu15: B
Secondary
alcohols are oxidised to ketones. Primary alcohols are
oxidised to aldehydes then carboxylic acids.
Qu16: B
2,4-DNP reacts with the carbonyl group in aldehydes and ketones
only.
Qu17: A
Both Kevlar and nylon contain repeating units joined by an amide
group, O=C-N unit and hence are polyamides.
Qu18: B
Terephthalic acid is 1,4-benzene dicarboxylic acid.
Qu19: A
Yes esters
are hydrolysed by water under acid or base conditions. You did it
under basic conditions in the laboratory and were asked to draw both
the acid and the base reaction mechanisms in the report.
Qu20: A
Do
you know your functional groups ?
Qu21: B
Since organometallic
compounds contain carbon - metal bonds and metals are more
electropositive than carbon, C-M systems are polarised such that the C
is negative and the metal is positive. Hence the C atoms of C-M
systems are nucleophilic.
Qu22: A
Review the experimental for this experiment.... the acid product
was obtained in the final step as a white precipitate by the
acidification of a solution containing the carboxylate salt.
Qu23: B
The dry glassware is needed because Grignard
reagents react with water.
Qu24: B
Grignard
reagents contain Mg.
Qu25: A
The first reaction is the addition
of bromine to a conjugated diene. At 50oC, this will be
under thermodynamic
control and so the initial product will be the 1,4-addition
product, 1,4-dibromo-2-butene. The resultant alkyl halide will
then react with excess CH3S- as a nucleophile (S is the same group as
O, and is a better Nu) to give the 1,4-dithioether, A. B would be the product of
kinetically controlled 1,2-addition of bromine in step one. All the
other products would require that more than 1 mole equivalent of
bromine were added to the diene.
Qu26: A
The most obvious structural feature in the product is the fused
cyclopropane ring - this has been formed in step 3, a Simmons-Smith
reaction - which adds a carbene type system to an alkene.
Step 2 would be consistent with that if it were an elimination
reaction, these strongly basic conditions would apply if we were
eliminating a halide.... this is fine since step 1 is a radical
bromination. Put this together, we need to take away the one
C atom added in the Simmons-Smith reaction to reveal the starting
alkene for that reaction = cyclopentene. Cyclopentene would be formed
by the elimination of bromocyclopentane which in turned would be
prepared from cyclopentane, A.
Qu27: C
Osmium
tetroxide reacts with alkenes to give 1,2-diols. Alcohols,
when heated with sulfuric acid react by dehydration to give alkenes
via an E1 type of mechanism which favour the most stable
products. A diol will give a diene, conjugated
dienes are often favoured because of their extra stability.
Although could be formed, there is a more stable and hence more likely
product. Epoxides as in B are
not usually prepared from diols. C
is a conjugated diene with two tri-substituted alkene units. D and E are more like the products of
alkene ozonolysis.
Qu28: B
The product is a cis-alkene, the last set of reagents indicate the catalytic
hydrogenation of an alkyne. The preceding steps look like a
terminal alkynes has been deprotonated with sodium amide, a
strong base
to give the acetylide ion, a good Nu and then reacted in an SN2 fashion
with the benzyl bromide to give the product. In order to get the
require alkyne for the reduction, the original alkyne needs to be
propyne, B. If A were the starting material, then
the product of the sequence would have one less C atom, Ph-CH2CH=CH2.
C, D and E are not
terminal alkynes and so would not react with step 1 and hence 2.
Qu29: D
The starting material is an alcohol, first set of reagents, sulfuric
acid and heat suggest dehydration
to give the alkene. Step 2 is ozone and step 3
corresponds to a reductive work-up overall an ozonolysis
reaction. The C=C has to form to give 1,1,3-triphenylpropene.
We are given the ketone product from the disubstituted end of the
alkene, the monosubstituted end will give an aldehyde under the
reducing work-up conditions, corresponding to phenylethanal, D.
Qu30: C
The product is an
epoxide and it has been formed by the reaction of a halohydrin.
Reaction of an alkene with a hypohalous acid gives a
1,2-halohydrin
followed by treatment with a base to allow an intramolecular SN2
reaction
(also an example of a intramolecular Williamson
ether synthesis) to
give
an epoxide. The starting material needs to be an alkene, so A, B
or C. In order to put
the epoxide in the correct location, the C=C needs to be in the ring
and be methyl substituted so 1-methylcyclopentene, C. A would give an epoxide but the
methyl group would be in the wrong location and B would also give an epoxide but it
would be external to the cyclopentane unit rather than on the
cyclopentane.
Qu31: A
The starting material is an alkyne, the first set of reagents indicate
a dissolving
metal reduction of an alkyne to the trans-alkene. The second
reagent is a peracid
and this will cause epoxidation of the alkene. This is a concerted
reaction and the stereochemistry of the alkene is preserved in the
epoxide. The final step, aqueous acid will cause the epoxide to undergo
acidic
ring-opening in an SN1like fashion to give a 1,2-diol. If you know
it gives a diol, A is the only
diol in the answers.
Qu32: AB
Reaction of an alkene
with a halogen in the presence of water gives a 1,2-halohydrin
followed by treatment with a base (sodium carbonate) allows an
intramolecular SN2
reaction
(also an example of a intramolecular Williamson
ether synthesis) to
give
an epoxide (hence answer must be A, B or C).
The reaction will lead to the halohydrin
via
the cyclic bromonium ion, the regiochemistry will put the -OH at the
more
substituted position with anti stereochemistry to the Br atom.
For the SN2 the
nucleophilic
HO must attack at 180 degrees (i.e. also anti) to the C-Br bond,
therefore the two
methyl
groups will still be trans in the product epoxide. So A
and
B both have the correct stereochemistry (they are the
enantiomers that correspond to the addition of the Br to opposite faces
of the alkene unit). C has
the wrong stereochemistry. D and E are diols not
epoxides.
Qu33: C
The product is a vicinal-dibromide (a 1,2- arrangement) so this must
come from an alkene rather
than an alkyne. Br2 adds
across
C=C to add one Br atom at each end of the pi
bond in an anti fashion. You should redraw the
product Fischer
diagram first as a wedge-dash
diagram viewed from the side then in a new wedge-dash diagram after
rotating about the central C-C bond to get the two Br anti (best to
draw the Br atoms in the plane of the page). This means that the two
alkyl groups
need
to be cis in the alkene as in C.
A would give a tetrabromide if there
were excess bromine or a vinyldihalide (Br-C=C-Br). B has
the wrong stereochemistry. D has too many C atoms, an ethyl
instead of a methyl group. E has the C=C in the
wrong location to give the required
product.
Qu34: DE
The starting material is an alkyne, the first set of reagents indicate
the catalytic
hydrogenation of an alkyne to the cis-alkene since poisoned
catalyst is being used. The second reagent is a peracid
and this will cause epoxidation of the alkene. This is a concerted
reaction and the stereochemistry of the alkene is preserved in the
epoxide. So because the alkene has cis methyl and phenyl groups, so
will the epoxide. A has one C
atom too few, the methyl group is missing. B and C have the groups in the wrong
stereochemistry, they are trans. D and
E are enantiomers with the
correct cis-stereochemistry formed by the O being added to opposite
faces of the C=C.
Qu35: B
This is a Diels-Alder
reaction.... hints are a substituted cyclopentadiene, the diene,
and a disubstituted alkene, the dienophile. Remember the reaction
is concerted and the stereochemistry of the diene and the dienophile is
preserved in the reaction. So because the dienophile is cis here, the
ester groups must also be cis in the product. The methyl group on the
diene needs to be tracked too. A has the cis ester groups but
has the less favourable exo product, B
is the correct answer with the cis ester groups in the favoured
endo
orientation and hence is the major product. C has
the ester groups trans and is therefore incorrect since the dieneophile
is cis. D has the
methyl group in the wrong location and E has lost the C=C that
needs to be present from the diene portion.
Qu36: C
The reaction is the hydroboration-oxidation
of an alkene. This gives the
anti-Markovnikov alcohol via a syn addition due to the concerted
addition
of the B and H across the C=C. Note that the -OH is formed with
retention
of stereochemistry when the B atom is replaced. So for
methylcyclohexene, the -OH ends up on the C next to the C-CH3
unit. Since the -OH and -H add syn, the -OH and the -CH3 must be
trans, C. A and B have the wrong stereochemistry. D has the wrong regiochemistry (this
is the Markovnikov product) and E
has the wrong functional group transformation.
Qu37: D
The starting material is an alkyne, the first set of reagents
indicate
the hydration
of the alkyne to give the ketone via the enol and the
tautomerisation. A and B are the enols that form, but
enols are very unstable and very rapidly equilibrate to the ketone, D. C
has the wrong regiochemistry since the +ve charge is most stable on the
benzylic C where it is resonance stabilised. E has one C
atom too few, a methyl group is missing.
Qu38: AE
Which systems are non-aromatic as drawn ? B, E,
AB and AE. B,
AB and AE are non-aromatic because the pi
system are not cyclic pi systems. B, E
and AB are all 6 pi electron
systems. Note that AC is
anti-aromatic, the empty p orbitals completes the cyclic conjugated
unit and it is a 4 pi electron system.
Qu39: A
or D or AD or BC or CD
Which systems are aromatic as drawn ? A,
C, D, AD,
BC, CD and CE. Now consider adding H+ to
make the conjugate acid.... the conjugate acids of C and CE are all still aromatic because
the protonated lone pair is not part of the pi system.
Qu40: B
or AE
Which systems are non-aromatic as drawn ? B, E,
AB and AE. Now consider removing H+
to make the conjugate base.... the conjugate base of AB would be a 8 pi electron
system.... tending to make it anti-aromatic.
Qu41: B
Which systems are non-aromatic as drawn ? B, E,
AB and AE. Tautomerism allows us to
move H atoms typically from heteroatoms to C trading pi bonds (as in
the ketone-enol tautomerism). This applies for B.
Qu42: C
Heteroaromatic means the ring contains a non-carbon atom. So that
limits us to B, C, CD,
or CE. Of these only C has the same number of electrons
as benzene.
Qu43: AD
Which systems are aromatic as drawn ? A, C,
D, AD, BC,
CD and CE. Which ones of these
are ionic i.e. charged ? AD or
BC. If n=1 in the Huckel rule
we need 4n+2 or 4x1 + 2 = 6 pi electrons. That's AD since BC is a 2 pi electron system.
Qu44: C
or CE
Which systems are aromatic as drawn ? A, C,
D, AD, BC,
CD and CE. Now consider adding H+ to
make the conjugate acid.... the conjugate acids of C and CE are all still aromatic because
the protonated lone pair is not part of the pi system.
Qu45: AC
The only anti-aromatic system here is AC. Which systems are
aromatic as drawn ? A, C, D,
AD, BC, CD
and CE. Which systems are
non-aromatic as drawn ? B,
E, AB and AE.