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: B
Allylic
hydrogens are found on the sp3 C immediately adjacent to a C=C
unit. i has 7 (CH3 and 2 x
CH2), ii has only 1 (a CH) and
iii has 3 (CH2 and a CH) hence i > iii > ii.
Qu2: A
Alkenes and alkynes react with aq. sulfuric acid to give carbocations
that then react with water as the Nu. Alkenes
give alcohols, alkynes
give enols that tautomerise to ketones. The rate determining step
is the
addition of the H+ to the pi bond and is controlled by the stability of
the resultant carbocation, so alkenes react faster than alkynes.
Alkanes are weak bases (so they do not protonate easily - where would
the electrons come from ?) so we have i
> ii > iii
Qu3: C
If you know your pKa's then this will help, remember that the
lower the pKa the stronger the acid. What if you don't remember
your pKas ? Then you'll need to deduce it. Think
of the simple acid equation HA <=> H+ A-
then look for factors that stabilise A-.... here we are looking at a
hydrocarbon, i corresponds to
a simple sp2 vinylic CH (pKa about 45) ii
is
an allylic position and iii is
a simple sp3 alkane type CH (pKa > 60). The key issue here is
that the allylic anion would be resonance stabilised, hence ii > i > iii
Qu4: A
Resonance
energies measure stability due to conjugation. If we look for
conjugation we see that i is a
conjugated triene, ii has
a conjugated diene and iii has
only isolated C=C (so it has
zero resonance energy as there is no resonance !). Therefore
we get i > ii > iii.
Qu5: D
Reaction is the Diels-Alder
reaction and we are looking at the dienes reacting with
CH2=CHCO2CH3 .... In order for the reaction to occur, the diene
needs to be s-cis. i is
locked s-trans (i.e. no free rotation), ii is locked s-cis so that's fine. iii can easily rotate around the
sigma bond to become the required s-cis. So ii > iii > i.
Qu6: E
All the CC bonds are between sp2 C atoms, the thing that is changing is
the type of bond between the C atoms involved in the bond. In i we have an aromatic bonds in
benzene, so it's about half way between a C=C and a C-C (about 140 pm).
In ii we
have a standard double bond (134 pm). In iii both C are sp2, but we are
looking at a C-C
between two C=C in a conjugated diene (about 146 pm).....so overall
iii > i > ii.
Qu7: C
Epoxidation
of an alkene.... more alkyl groups makes the alkene more
nucleophilic because alkyl groups are weak electron donors. i is disubstituted, ii is trisubstituted and iii is monosubstituted so reactivity
is ii > i > iii
Qu8: C
Reaction
is the addition of HCl to an alkene. This gives the Markovnikov
alkyl chloride via the most stable carbocation
intermediate. First draw phenylethene C6H5CH=CH2, then add the H+
to the least substituted end of the C=C to give the more stable
conjugated and hence resonance stabilised carbocation,
C6H5CH(+)-CH3. So ii is
the major
product
and i is a minor product
(the anti-Markovnikov product). iii
not formed... it destroys the aromaticity. Overall then ii > i > iii
Qu9: B
Sucrose is the disaccharide of glucose and fructose, they are the
component monosaccharides.
Qu10: A
Qu11: A
An anomeric carbon is typically attached to two oxygen atoms by single
bonds, here a OH group and a OC group
Qu12: B
Reactions are first order if the rate law has depends on the
product of the concentrations of a single molecules. If a
reaction depends two molecules of A (i.e. rate = k [A] 2 )
then that reaction is second order.
Qu13: A
Alcohols
undergo dehydration, an elimination with strong acid via the E1
pathway via C+ intermediates.
Qu14: A
The reaction
of alcohols with HCl in the Lucas test is an SN1 type reaction and
forms the alkyl chloride. These are less polar than alcohols and tend
not to be soluble in the aqueous medium.
Qu15: A
Tertiary
alcohols are
not easily oxidised to carbonyl compounds.
Qu16: A
2,4-DNP reacts with the carbonyl group in aldehydes and ketones
only.
Qu17: B
Nylon [6.6] is made from a diacid system with 6 carbons and a
diamine containing 6 carbons.
Qu18: A
For example, the an ester synthesis : RCO2H + R'OH-->
RCOOR' + H2O.
Qu19: A
Yes - this causes the solvent to condense and run back in to the
flask so that it does not boil dry.
Qu20: A
Do
you know your functional groups ?
Qu21: A
Grignard
reagents contain Mg.
Qu22: B
No the iodine actually reacts with the Mg.
Qu23: A
This is typical of work-up... neutralise the reaction conditions
to allow the easy isolation of a neutral organic molecule.
Qu24: A
Grignard
reagents contain Mg.
Qu25: C
Working forwards....the first reaction is the addition
of hydrogen bromide to a conjugated diene. At -80oC,
this will be
under kinetic
control and so the initial product will be the direct or
1,2-addition
product and will have the Br derived from the more stable C+
location. A has added
the HBr 1,2- but in an anti-Markovnikov fashion, B is the thermodynamic product from
1,4-addition. D
and E don't make any
sense....they would require vinyl and primary carbocations be formed.
Qu26: D
Working backwards.... look at the product (note it's C7) and the
reagents... ozonolysis
with a oxidative work up... reconnect the two carbonyl groups to
get the require alkene, ethylcyclopentene. This would be formed
by the dehydration
of an alcohol. The only alcohols are A, D
and E. However A and E will not give an ethyl substituted
system and E is only C6.
Qu27: D
Working forwards....the reaction is the oxymercuration
- demercuration of an alkene.... gives an alcohol following Markovnikov's
rule, no carbocation rearrangements. Probably a good idea to
draw out the alkene starting material in the same type of line diagram
as the products...
The only alcohols are C, D and E. C requires a rearrangement via a
1,2-alkyl shift of a carbocation intermediate and E is the anti-Markovnikov product.
Qu28: A
Working backwards.... look at the product : it's C7 and a methyl
ketone, 2-heptanone, formed by the hydration
of an alkyne. The options A
- E allow for heptyne to be
made with the triple bond at C1 to C5 respectively. The most
efficient synthesis will be from 1-heptyne so that the methyl ketone is
the major product since the alkyne would be terminal. 2-heptyne
(from B will give a 50:50
mixture of the required product and 3-heptanone.
Qu29: B
The transformation is alkene to alkyne, to make pi bonds, we usually
use eliminations... so we need to get some leaving groups in and then
take them out.... if we remove the C=C we need to then make two new pi
bonds... hence two leaving groups are needed..... two halogens is
probably the best choice then need a strong
base for the E2 eliminations of the halides. A will give an alkyl bromide then an
alkene, C will give an alkane
via addition, D will give an
alcohol then an alkene and E
will not cause an elimination as there is no -OH leaving group.
Qu30: E
Working backwards.... look at the product...this is a Diels-Alder
reaction.... hints are the cyclohexane units. The key is to
recognise that the diol coming from an alkene (the cyclohexene unit) by
the permanganate
reaction. If you draw that in, then you can push the curly arrows
to "reverse" the Diels-Alder and reveal the diene and the dienophile.
Qu31: D
See Qu 30.
Qu32: E
The starting material is an alkyne, the first set of reagents
indicate
a dissolving
metal reduction of an alkyne to the trans-alkene. Alkenes
react with aq. acid to undergo additions to alcohols in accord with
Markovnikov's
rule, based on the resonance stabilisation of the carbocation
intermediate, E is the correct
answer. A, B and C could only come from an alkyne, D has the wrong regiochemistry.
Qu33: C
Reaction of an alkene
with a halogen in the presence of water gives a 1,2-halohydrin
via a cyclic bromonium ion, the regiochemistry will put the -OH at the
more
substituted position with anti stereochemistry to the Br atom and the
-OH group. A has the wrong
regio- and stereochemistry,
B has the wrong regiochemistry,
D has the wrong
stereochemistry, and E has the
wrong regiochemistry.
Qu34: B
Radical addition of two equivalents of HBr across an alkyne gives a
1,2-dibromide. Look at the mechanism and remember that (i) Br can
stablise a radical (like it does a C+) and (ii) that it is the Br
radical that adds first to the alkyne and then to the alkene in the
second reaction.
Qu35: B
This is a Diels-Alder
reaction.... hints are the dienophile, and the bridged structure of
the product. The challenge here is to realise that the C=C
has been removed by the catalytic
hydrogenation... the only way to recognise where it was it to
recall that it is opposite in the cyclohexane unit to the location of
the dienophile which is easily recognised by looking at the ester
groups. With the C=C back in place, then you can push the curly arrows
to "reverse" the Diels-Alder and reveal the diene. A lacks the O atom, C has the methyl group in the wrong
location, D lacks the methyl
group altogether and E is not
a diene.
Qu36: C
Osmium
tetroxide reacts with alkenes to give 1,2-diols. The product is a
geminal-diol so this must
come from an alkene rather
than an alkyne. The -OH groups are added
across
the C=C in a syn 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 -OH syn (best to
draw the OH groups in the plane of the page). This means that the two
alkyl groups (one methyl and one ethyl)
need
to be cis in the alkene as in C.
A is an alkyne. B has
the wrong stereochemistry. D and E have too few C atoms, an methyl
instead of an ethyl group.
Qu37: E
The reaction is the hydroboration-oxidation
of an alkene to give 3-methyl-2-pentanol. The reaction 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. Redraw one of the
enantiomers so the -OH and the H that added are syn then remove them to
reveal the C=C unit. A and B would give
2-ethyl-1-butanol. C would give 3-methyl-1-pentanol. D
has
the wrong stereochemistry.
Qu38: C
Which systems are non-aromatic as drawn ? A, C,
E, AB, CD
and DE. Of these A, C,
E, AB and DE are non-aromatic because the pi
system are not cyclic pi systems. Only C is a 4 pi electron
systems.
Qu39: A
In order to be non-conjugated, need either an alkene or an isolated
polyene.
Qu40: E
Which systems are non-aromatic as drawn ? A, C,
E, AB, CD
and DE. To be a triene
we need 3 x C=C as in E. CD and DE are not trienes, they are
dieneones.
Qu41: E
or DE
Which systems are non-aromatic as drawn ? A, C,
E, AB, CD
and DE. Tautomerism
allows us to
move H atoms typically from
heteroatoms to C trading pi bonds (as in
the ketone-enol tautomerism). This applies for DE. But it could also apply
occur in E in a hydrocarbon
variation.
Qu42: AC
or AE
Which systems are aromatic as drawn ? D,
AC, AD, AE,
BC and CE. If n=2 in the Huckel rule we
need 10 pi electrons. D, AD, BC
and CE have 6 pi electrons in
their aromatic systems.
Qu43: C
Look for a non-aromatic system with an aromatic conjugate
base....Which systems are non-aromatic as drawn ? A, C,
E, AB, CD
and DE.
Which are hydrocarbons ? A, C, E
and AB. Which will have
aromatic conjugate bases ? C
and E. Both A will have anti-aromatic conjugate
bases. AB will have a
nonaromatic conjugate base.
Qu44: AD, BC or CE
Which systems are aromatic as drawn ? D,
AC, AD, AE,
BC and CE. If n=1 in the Huckel rule we
need 6 pi electrons = D, AD, BC
and CE. Now
consider adding H+ to
make the conjugate acid.... the conjugate acids of D and CE are all still aromatic because
the protonated lone pair is not part of the pi system.
Qu45: AB
Which systems are non-aromatic as drawn ? A, C,
E, AB, CD
and DE. Now consider
adding H+ to
make the conjugate acid.... the conjugate acids of AB would be aromatic because
the C+ would form at the tertiary C in conjugation with the 3 C=C in
the 7 membered ring, where n=1 in the Huckel rule.