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: E
Acidity...all
the H we are interested in are located on N atoms, the difference is
the number of C=O groups in proximity. Each C=O allows us resonance
stabilisation via delocalisation of the -ve charge in the conjugate
bases to the electronegative O atom (in the same way as for a simple
carboxylic acid). Thus iii
> i > ii.
approximate pKa's iii = 16, i = 30, ii = 35
Qu2:C
Since the +ve center is not adjacent to the benzene ring, the question
is really comparing a secondary, a tertiary and a vinyl cation.
Since alkyl groups are weakly electron donating due to hyperconjugation
and polarisation effects, more alkyl groups give a more stable
carbocation. Hence tertiary cations are more stable than secondary
cations. Vinyl cations are quite unstable due to the nature of
the empty orbital. So ii >
i > iii.
Qu3:C
i is a simple amide, ii is a simple ketone, if you know
it, these are about 1660 and 1715 cm-1 respectively (or use
the tables). iii is has
the C=O with 2 NH groups, one either side. In an amide, the N donates
electrons via resonance to the C=O which increases the single C-O
character and so lowers the carbonyl frequency. This is effect is even
more pronounced with the two N atoms in iii, therefore ii > i > iii.
Qu4:C
The reaction of alcohols with HBr is essentially an SN1 type
reaction and hence depends on the stability of the carbocation
produced. i is primary,
ii is secondary and iii is an aromatic alcohol.
Remember that the C attacked in SN reactions need to be sp3 ? Hence ii > i > iii.
Qu5: A
Each type of carbon will give a single peak. i has 5 types, ii has 4 and iii has 2 types so i > ii > iii.
Qu6: E
13C nmr spectroscopy... We are looking at 3 different methyl groups
next to 3 different C=O groups. What's the effect ? The more electron
withdrawing the C=O group unit, then the great the deshielding and
therefore the greater the chemical shift of the methyl group.
Remember that the N of an amide is an electron donor via
resonance. The shifts are 31ppm, 22 ppm and 34 ppm respectively,
so iii > i > ii.
Qu7: E
H nmr spectroscopy.... We are looking at the effect of a CH2 group that
is attached to a -Cl and another but different group... benzene, H and
OCH3 respectively. The O in iii will deshield due to the
electronegativity of the O. Benzene rings cause a little
deshielding due to the magnetic anisotropy. H exerts no
electronic effect (it's the normal situation), so iii > i > ii.
Qu8: AB
The reaction here is SN2, so it will depend on the degree of steric
hindrance at the C-LG center. i
is tertiary (hence slow), ii
is secondary and iii is
primary (hence fast) so iii
> ii > i.
Qu9: C
A good leaving group is the conjugate base of a strong acid (i.e.
stable is the displaced form). Acidity increases down the groups
of the periodic table so H2S is more acidic than H2O so HS- is a better
LG than HO-. HI is a very strong acid and hence iodide, I-, is a
very good leaving group. So ii
> i > iii.
Qu10: AB
Straight from the midterm ! Basicity...
the strongest base will create the most of the
conjugate base. Compare to O systems first... O- is a stronger base
than O, so ii > i. Now compare N- and O-
. N is less electronegative than O so it is a better electron
donor and hence a better base (Lewis definition) so iii > ii. Therefore overall iii
> ii > i
Qu11: AB
Elimination of alkyl halides is via the E2 pathway, where the H
is always removed from the C adjacent to the C-X bond. Hence, i can only give one alkene product,
1-pentene. ii can
eliminate to give 2-pentene, but this can exist as a mixture of cis and
trans isomers. iii can
eliminate to give 3 alkenes.... 2-ethyl-1-butene, cis-3-methyl-2-pentene and trans-3-methyl-2-pentene. Hence iii > ii > i.
Qu12: B
Radical stability follows the same trend as carbocation
stability (since both deal with alkyl groups stabilising electron
deficient centers). Here we have tertiary, primary and secondary
respectively so the stability order is i
> iii > ii.
Qu 13:D
Rf is the ratio of distance traveled by sample to distance
traveled by solvent from the origin. Measure these distances with
a ruler. Distance traveled by sample (middle of spot) = 17mm,
distance traveled by solvent = 34mm therefore 17/34 = 0.5
Qu14:A
If the sample shows up as two spots after development then is
must contain at least two compounds, hence the sample is impure so i is true. The spot that is more
polar in normal chromatography will have a lower Rf value since it will
interact with the polar stationary phase more, so ii is incorrect. The spot that
elutes more rapidly is the one that moves the fastest i.e. travels the
furthest, This is x so iii is
false.
Qu15:BCE
A is false because benzene has
an IHD of 4 due to 3 C=C and one ring. D is false because glycine does not
have a chirality center with 4 different groups attached.
Qu16:BCD
A is false because acetone is a polar, aprotic solvent. E is false because this reaction
reflects SN2 reactivity and that means the less hindered system will
react the most rapidly.
Qu17: BD
A is false because it reacts to give an alkyl bromide, alkenes
react to give 1,2-dibromides. C
is false because methylbenzene reacts to give a resonance stabilised
secondary radical rather than a simple secondary radical. E is false because the low
reactivity is due to the lack of a benzylic H and hence the low radical
stability.
Qu18: B
The heat of formation... more exothermic means a more stable
compound, -13.5 kcal/mol is the most exothermic. So if we are looking
for the most stable isomers, this will be the one with the two
substituents in the more favourable equatorial positions, hence B.
Qu20: D
The isomer with the most Van der Waals strain will be the one
with the most 1,3-diaxial strain, that will be the one with the
substituents axial, D.
Qu21: B
or D
A constitutional isomer has different connectivity due to
different branching and / or different functional groups... but of
course they have to have the same molecular formulae to be
isomers. A is the same
as the question, C is
stereoisomer and E is not an
isomer (C5).
Qu22: B
or D
A conformational isomer has the same connectivity but is different due
to rotation about single bonds... but of course they
have to have the same molecular formulae to be isomers. A and C are constitutional isomers and E is not an isomer (C5).
Qu23: D
There are two chirality centers, one at C6 and one at C7. Hence
there are 22 optical isomers.
Qu24: C
The are 4 types of C in the aromatic ring. There are 2 equivalent
ethyl groups attached to the N, so we are up to 6 total. Then there is
the C=O, plus 3 more in the cyclopropane ring and a the C attached to
the amine. That is a total of 11.
Qu25: B
O5 is part of a double bond,
C=O, so it is sp2. C7
is sp3 because it has 3 C and 1 H attached, hence 4 single bonds.
N9 is sp3 because it
has a C atoms
attached, 2 H atoms and the N lone pair but there is not resonance
since there
is not adjacent pi system, it's an amine N.
Qu 26: B
Oxidation
states
C4 has the following bonds : 1 x C (count 0) and 2 x O (count
-2) and 1 x N (count -1) so the
sum = -3 therefore the oxidation state of C4 = +3.
C7 has the following bonds : 3 x C (count 0)
and 1 x H (count +1) so the
sum = +1 therefore the oxidation state of C7 = -1.
Qu 27: C
A ethyl group requires a triplet and a quartet. The quartet is
for the CH2 coupled to the CH3, but because the CH2 is also attached to
the electronegative N atom, is will have the greater chemical
shift. Since other H on the molecule only has one of that type,
the integral for the ethyl group will be 4:6 (note we also gave full
marks for AB, but C is the best answer).
Qu28: D
Working backwards, the second reaction is an SN2 to replace the a
leaving group with a -CN. The leaving group turns out to be
a Br, put in place by a radical
halogenation of alkane type CH at the most stable radical site
(bromine selectivity). Alcohols A
and C may react in both steps
but the -OH group (poor LG) would still be present in the product.
Alkene B would react with the
Br2 to give a dibromide. So this leaves D or E. Counting carbons shows that we
need a C2 side chain.
Qu29: D
The first reagent is tosyl chloride, TsCl, so we are making
a tosylate of an alcohol, ROTs. That narrows the choices to B, C
or D. This is followed by an
SN2 reaction to give the iodide. Since stereochemistry is implied in
the product, we need to pay attention to that. When an alcohol
reacts with TsCl the C-O bond in the original alcohol is unchanged and
therefore the stereochemistry in unchanged in that step. However,
SN2
reaction usually occur with inversion so the stereochemistry of the
final iodide is the opposite to that of the original tosylate and hence
alcohol. B will give a
racemic product, C will give
the enantiomer of the required product, whereas D gives the highest yield of the
required product.
Qu30: D
PCl3
reacts with alcohols to give alkyl chlorides via an SN2 type
reaction. This chloride would then react with the ethoxide to
give a ether via a Williamson
ether type synthesis, another SN2 reaction. Ethoxide will not
substitute a aryl chloride (since the C is not sp3) - this rules out C and E.
A and B require an oxidation, but we do
not have an oxidising agent here.
Qu31: E
A simple alkyl
bromide being heated with a sterically hindered base under aprotic
conditions suggests an E2 reaction to give an alkene rather than a
substitution. That limits the answer to C, D
or E. Since E2
reactions occur in such a way that the LG and H are lost from
adjacent carbon atoms (i.e. they are 1,2-elimination reactions), then E is the only viable answer.
Qu32: A
Another alkyl
bromide being heated with a base - again an E2 reaction to give an
alkene rather than a substitution. Since the base here is
hydroxide (hence small and unhindered), the product should follow
Zaitsev's rule and give the more stable, more highly substituted
alkene. This means either A or
B is our answer, but which ? C and D are substitution products, E has too many C atoms. In order to
select between A and B we need to look at the
stereochemistry.... remember that an E2 requires that the H and the LG
are at 180 degrees. If we set up the starting material in this way then
the methyl groups will end up trans
as in A rather than cis as in B.
Qu33: A
We need to convert the alcohol to an ether with 2 more carbon
atoms and a nitrile group. A
is a Williamson
ether synthesis... make the -OH into the alkoxide, a better Nu,
then SN2 reaction where the iodide (better LG) is displaced. In the
final step the -CN replaces the -Cl in another SN2 reaction. B step 1 may react to give the -CH2OCH2CH2OH
side chain but then would not react with the NaCN. C step 1 would react to place a Br
on the cyclohexane and step 2 may react to give a disubstituted
cyclohexane. D step 1 would
give the cyclohexyl tosylate, but then that would not react with the
BrCH2CH2CN (where is the Nu ?). E step 1 alcohol to bromide, step 2
bromide to alkene... step 3 no reaction.
Qu34: B
Overall reaction alcohol to alkene - hence a dehydration, an
example of an elimination. Note that we want the less highly
substituted alkene, so regular conc. acid / heat (E1) is not going to
work because that would give 2-pentene and not the 1-pentene required. A HBr cause substitution to give
alkyl bromide... any elimination would give 2-pentene. B step 1 reacts to give the
tosylate which is then reacted with a hindered base via an E2 to give
the required product. C would
react to give 2-pentene. D HBr
cause substitution to give alkyl bromide, but the ethoxide / ethanol
reaction would give a lot of substitution and a mix of alkenes if there
is any elimination (heating with a more hindered base would have worked
though). E no reaction.
Qu35: B
Need to make a thioether from an alcohol, need to get the
opposite stereochemistry - hence avoid SN1 and force SN2. A HBr causes substitution to give
alkyl bromide but via an SN1 so we would get racemic bromide and hence
racemic thioether. B step
1 reacts to give the tosylate which is then reacted with the thiolate
nucleophile via an SN2 (hence inversion) to give the required
thioether. C Poor reaction,
Sn1 character, hence racemisation will occur. D or E will not convert the -OH into a
better leaving group hence no substitution.
Qu36: B
Need to replace the -OH with a -Br with a change in the carbon
skeleton... hence via a carbocation rearrangement (an alkyl shift)
hence need an SN1 type reaction. A, C and D are SN2 reactions therefore the
Br will end in the same location as the original -OH with no change in
the skeleton. B Perfect
! E will add a Br via
radical substitution in a different location, the OH would still be
present and there would be no carbocation and hence no rearrangement.
Qu37: A
4 ArH each of an individual type implies either ortho or meta disubstituted aromatic (6.8 -
7.13 ppm). 3H singlet at 3.8ppm suggests OCH3 group. IR says no
C=O or OH. 13C also lacks a C=O and has 6 types of ArC.
Qu38: AB
4 ArH of 2 individual types suggests a para disubstituted aromatic (7.2 -
7.8 ppm). No peak above 9ppm means it's not an aldehyde or an acid
(hence rules out C or AD). IR shows a C=O but no O-H or
C-O. 13C shows C=O at 197.5ppm (implies ketone or aldehyde). The lack
of a peak near 4ppm in the Hnmr rules out the esters D and E and the ethers A and AC.
Qu39: D
4 ArH each of an individual type implies either ortho or meta disubstituted aromatic (7.1 -
7.9 ppm). No peak above 9ppm means it's not an aldehyde or an
acid (hence rules out C or AD). IR shows a C=O and C-O but not
O-H. 13C shows C=O at 167ppm (not a ketone or aldehyde). 3H
singlet at 3.9ppm suggests OCH3 group suggesting the esters D and E (ruled out because it's para) or ethers A and AC (ruled out because these lack a
C=O).
Qu40: AD
4 ArH of 2 individual types suggests a para disubstituted aromatic (7.3 -
7.9 ppm). Peak at 12.8 ppm that is exchangeable means a
carboxylic acid (AD is the only
one).
IR shows a C=O and O-H and C-O. 13C shows C=O at 167.3 ppm (implies
acid or derivatives). AE
lacks the C=O.
Qu41: AC
4 ArH of 2 individual types suggests a para disubstituted aromatic (6.8 -
7.05 ppm). No peak above 9ppm means it's not an aldehyde or an
acid (hence rules out C or AD).
IR shows no C=O or O-H but indicates a C-O. 13C shows no C=O.
Absence of C=O leaves us only A,
AC and AE. lack of an OH rules out AE.