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: C
The
reaction is nucleophilic
addition to carbonyl groups, looking at the relative
reactivity of aldehydes (i and ii) and ketones (iii). Electronic
and steric factors mean than the number of alkyl groups are important :
they both make the carbonyl C less electrophilic and more hindered
hence less reactive so we get ii >
i
> iii.
Qu2: C
The reaction is electrophilic aromatic substitution, and we need to
look at the substituent
effects on the aromatic ring. The -OC(=O)CH3 group
in i is attached to the ring
via the O attached by single bonds (i.e. the alcoholic O) of this ester
group. This O has then lone pairs that can be donated to the ring
and hence it is an electron donating group and hence is an
activator. The -OH group in ii
of course all has then lone pairs that can be donated to the ring
and hence it is an electron donating group and hence is also an
activator. What's the difference ? In the ester in i the O lone pair is also involved
in resonance with the C=O group, which makes the lone pair less
available for donation to the aromatic ring. The -CF3
in iii is a
deactivating group due to electron withdrawal by strong
inductive
effects due to the electronegativity of the F atoms. So the reactivity
is ii > i > iii.
Qu3: A
If you know your pKa's then this is easy : ammonia = 35, terminal
alkyne
pKa = 26, t-butanol
= 18. Remember the lower the pKa the stronger the acid, so i > ii > iii.
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 ammonia and
the alcohol.... if you recall, N is less electronegative than O so N is
less stable as an anion compared to O, hence alcohols are more acidic
than ammonia. 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
Enols of active
methylenes (where there are 2 C=O groups separated by a CH2
group) are more stable than those of simple carbonyls, one reason being
the possibility of a
very favourable if the 6 membered ring, as would be the
case here for both i and ii. The difference here
between these two is the degree
of substitution of the alkene unit.... more alkyl groups make it
more stable. So the dialkyl-substituted alkene in i is more stable than the
monoalkyl-substituted alkene in ii.
So we have i > ii > iii.
Qu5: E
Electrophilic
addition to C=C in a series of substituted alkenes with HBr = hydrohalogenation
reaction . Reaction is controlled by the stability of the
intermediate carbocations formed by the addition of the H+ to the
C=C. System iii gives a
tertiary carbocation where the
lone pairs on the adjacent O in the ether group can give some extra
resonance stabilisation. System ii
gives a secondary cation, and
iii gives a secondary
carbocation where the
lone pairs on the adjacent O in the ether group can give some extra
resonance stabilisation (an electron donating group). Remember that the
more stable cation is the easiest / fastest
to form, so iii > i > ii.
Qu6: C
Look at how the stability of the deprotonated form changes (i.e. the
conjugate base using the
simple acid equation HA <=> H+ A-
then look for factors that stabilise A- ). So look at the
stabilisation of the charge and the way
this is influenced by the aromatic substituent
effects. Remember simple
electrostatics
(like charges repel = destabilise). -OCH3 in iii is an
electron
donating group by resonance = decreased stability, -NO2 in ii is
strongly
electron withdrawing due to resonance and inductive effects, and H
in i is electronically
neutral (i.e. no effect). Overall then we have ii > i > iii.
Qu7: B
Remember the rules
for ranking resonance structures : complete octets are most
important...draw a Lewis structure complete with the lone pairs
first. If we look at i has
complete octets at C, N and O despite the charges, and note it has one
more pi bond than the other two. As for the other two, the
negative charge on the more electronegative O atom is more
important. So i > iii > ii.
Qu8: A
The systems are all organometallic
reagents where the C atoms react as nucleophiles.
Either look at the reactivity of the metal in its elemental form or
consider the electronegativity. The more reactive the metal itself, the
more reactive the organometallic reagent. So overall then i > ii > iii.
Qu9: C
The reaction is electrophilic
aromatic substitution, a nitration,
we need to consider the directing
effects of the substituents. The two C=O systems are both meta- directing and the Br is ortho-/ para- directing, hence the
major product will be at site ii.
Steric effects of the larger tBu group will make iii less reactive than i. So the yields are such that ii > i > iii
Qu11: B
The pKa is more like 12. It's an active
methylene, and you used ethoxide (pKa = 16) to deprotonate it.
Qu12: B
The balanced equation is : 2 Na + 2 CH3CH2OH
-> 2 CH3CH2ONa + H2
Qu13: B
The structure shown is ethyl acetoacetate. Diethyl malonate is the
diester = CH3CH2O2CCH2CO2CH2CH3
Qu14: B
The iodide reacts with the butyl bromide to make butyl iodide
via an SN2 reaction.
Qu15: B
Ethoxide and methoxide have very similar basicities, the reason is to
avoid transesterification.
Qu16: B
The chemical shift for the CH unit at 4.2 ppm and the CH2O
units at 2.9 ppm are incorrect for diethyl n-butylmalonate.
Qu17: B
2,4-DNP only reacts with aldehydes and ketones not acids or
esters.
Qu18: A
Qu19: B
The Lucas test depends on SN1 type reactivity. Phenols do not
react via the SN1 pathway due to the unfavourable phenyl cation that
would be required.
Qu20: A
Qu21: C
B, D and E are all amines. A is really an imide.
Qu22: ABCDE
Count the attached groups including lone pairs but remember to
consider the impact of resonance. If the N is adjacent to a pi
system then it will be involved in resonance and hence the lone pair
will be in a p orbital. In E the N is part of a double bond.
Qu23:
BDE
Review
aromaticity ?
Qu31: D
The first step is ozone with and a reductive work-up overall an ozonolysis
reaction, cleaving the alkene to give 2 molecules of the ketone
acetone. The Grignard
reagent is then added to the
ketone carbonyl followed by a normal dilute acid work-up to give the
tertiary alcohol.
Note : only D is a tertiary
alcohol. Count C atoms !
Qu32: D
The starting material is a ketone. Reagent 1 is lithium diisopropyl
amide (LDA), a strong non-nucleophilic base - this will react with the
ketone to form the enolate. Reagent 2, methyl iodide will react
with the enolate in an SN2 reaction to give the alkylation product
where a methyl group has been added adjacent to the carbonyl
group i.e. alkylation
of an enolate. Reagent 3, sodium borohydride, NaBH4,
will reduce
agent the ketone
carbonyl to a secondary alcohol. C
is a tertiary alcohol and has the methyl group at the wrong location.
Qu33: A
The first reaction will the electrophilic addition of the HBr to
the alkene in accord with Markovnikov's
rule, so giving
2-bromopentane. Reaction of this alkyl bromide with triphenyl
phosphine and a strong base will form an ylid for a Wittig
reaction -
this is completed when the carbonyl is added ... the product will be
the alkene where the new C=C is formed between the original carbonyl C
and the C-Br center. B has the
wrong C=C location (moved in ketone portion), C has the C=C to the wrong carbon of
the alkyl bromide. D and E have the wrong transformation.
Qu34: C
The benzene ring will react with the anhydride via a Freidel-Crafts
acylation reaction to give the ketone. Treatment of the ketone with Zn
/ Hg / HCl is a Clemmensen reduction which converts the C=O to a CH2.
i.e. ethylbenzene in this case. The final step is a
Freidel-Crafts alkylation reaction to give para-ethylmethylbenzene, C, directed by the o/p directing
effect of the ethyl group.
Qu35: E
This is a Diels-Alder
reaction.... hints are the cyclohexadiene, the conjugated diene,
and a substituted alkene, the dienophile. Remember the reaction
is concerted and the stereochemistry of the diene and the dienophile is
preserved in the reaction. Only A,
D and E correspond to DA reactions of
cyclohexadiene. B and C are from reactions of
cyclopentadiene (count the C atoms). A
has trans-acid groups so it
has the wrong stereochemistry from the
cis-dienophile. D has
the wrong functional groups.... aq. acid will hydrolyse
the anhydride from the dienophile not reduce it.
Qu36: C
The Grignard
reagent will add to the epoxide at the least hindered end (since we
have a strong Nu, the reaction is SN2 in character). This reaction is
completed via a normal acid work-up giving an alcohol. Step 2 is
a Williamson
ether synthesis - conversion of the alcohol to an ether : Na
removes the proton generating the alkoxide that reacts in an SN2
reaction with the alkyl iodide. The only products that are ethers
are C and E. E
has the wrong regiochemistry based on the Grignard step.
Qu37: E
The starting material is an aldehyde and an ester. The 1,2-diol
in the first reagents will react with the aldehyde to form a cyclic
acetal, a common protecting group for aldehydes and ketones. Step
2 is lithium aluminium hydride, a strong hydride reducing agent - this
will reduce
the ester group to a primary alcohol. Step 3 removes the
protecting group to reveal the aldehyde. Need a C4 system or only
E is an aldehyde !
Qu38: B
The product is a cyclic acetal formed by the reaction of a 1,2-diol
with a ketone. : see the ketone, acetone in step 2. In
step 1, osmium
tetroxide reacts with an alkene to give 1,2-diols. Hence we
need an alkene. C is a
diene, the extra C=C would either react or should still be there.
Qu39: A
Really need to work backwards with this one. Step 2 will add
Br to aromatic rings : need to check the regiochemistry. The right
hand aromatic ring has an alkyl group (o/p) and a nitro group (m) - so
this is consistent. The left hand ring also has a alkyl group and an
alkoxy group (both o/p), again consistent. So the 2 Br atoms could be
added in this step, or one could be in place already, if that's the
case, then the relative reactivity of the two aromatic rings will come
into play = substituent
effects. The right had has the nitro, a deactivating group
and the left has an alkoxy group, an activator. Step 1 is a Williamson
ether synthesis : base (K2CO3) then
alkyl iodide - this converted a phenol to a methyl ether. Only A,C
and D are alcohols for step 1.
D lacks the methyl group meta
to the ether in the product, so that can't be right. In C the problem will be further
bromination of the top ring.
Qu40: C
Step 3, PCC = pyridinium chlorochromate, an oxidising
agent for alcohols. Step 2.... oxymercuration ..... looks
like of an alkyne (peek at step 1) to give a ketone most likely, and
step 1 looks like the acetylide has been added to a carbonyl giving an
alcohol. If we look at the product, then the (O=C)CH3
unit on the right has come from the alkyne, so we need the C6H5CH2CHO
starting material = C. A would react with 2 eq. of
the acetylide or give a mixture of products. B the acidity of the -OH would just
protonate the acetylide. D
would give a tertiary alcohols that would not be oxidised and E lacks a carbonyl for the acetylide
to react with.
Qu41: A
Not an easy one.... need to spot the condensation - the "hint" is
that step 1 is an alkoxide base and all the possible starting materials
are carbonyl compounds. Counting C atoms may help.... It needs to be an
ester then to get to the right oxidation state - so a Claisen
condensation followed by decarboxylation.
B and E would undergo aldol reactions to
give a beta-hydroxy carbonyls - and the product would have too many C
atoms. C would just be
deprotonated by the base, D
lacks an alpha-H so it can't form an enolate.
Qu42: D
The product is a cyclic ester..... step 4 probably formed this from the
corresponding acid and alcohol - break the ester to see that. Sodium
borohydride, NaBH4, is a reducing
agent for aldehydes and ketones. Since the alcohol needed is
secondary, it requires that it was a ketone that was reduced. The
ketone and the acid were formed by the ozonolysis
with an oxidative work-up (hydrogen peroxide) of an alkene.
Counting C atoms eliminates B
and C as answers. Since A is a diene the ozonolysis will
remove 3C atoms as a dicarbonyl by product. E would give an isomeric
(regioisomer) product.
Qu43: C or D
Step 2 is the oxidation of an aromatic alkyl group to give a
carboxylic acid. Step 1 could be either a Friedel-Crafts
alkylation or an acylation
using either an alkyl halide or an acyl halide respectively. This
narrows the choices to B, C
or D. However, it can't be B since the tert-butyl group does not oxidise to the carboxylic acid since it lacks a benzylic H. Both in fact would work
since aromatic ketones can be oxidised to carbooxylic acids (infact the
oxidation of alkyl aromatics to aromatic acids probably occurs via
alcohols and aldehydes / ketones).
Qu44: B
Step 3 is a chromium oxidation of a primary alcohol or an aldehyde
to give the carboxylic acid. Steps 2 and 1 correspond to a hydroboration
/ oxidation to give the primary, anti-Markovnikov alcohol from the
alkene. D is the first to go
- it's not an alkene. E has
too many C atoms. A and C have the wrong alkene
regiochemistry.
Qu45:D
Protect the ketone as this cyclic
acetal needs the 1,2-diol : HOCH2CH2OH
/ H+
Qu46: BC
Need to convert the alkene to an anti-Markovnikov
alcohol : hydroboration
/ oxidation
Qu47: AB
Convert the alcohol
to a bromide - remember -OH is a poor leaving group so E will not work, use PBr3.
Qu48: ABC
Carboxylic
acid to an ester : need the right alcohol and an acid catalyst.
Qu49: DE
The ester has been acylated i.e. the CH3C=O group
has been added.... a Claisen
condensation of an ester with a second molecule of itself - so we
need a base, the corresponding alkoxide being the best choice - it's an
ethyl ester so use ethoxide.
Qu50: DE
The active
methylene has been alkylated, looks like an enolate question so we
need need a base, the corresponding alkoxide being the best choice -
it's an ethyl ester so use ethoxide (again !)
Qu51: CD
We have removed the ester group.... remember beta-ketoesters
can be hydrolysed and decarboxylated : here best to choose basic
conditions to avoid deprotecting the acetal system at the same time.
Qu52: AC
The ketone has been converted to an alkene with one C added, a Wittig
reaction.
Qu53: C
Now convert the alkene to an epoxide = epoxidation
= use a peracid
Qu54: BE
Open the epoxide
to make a 1,2-diol and deprotect
the cyclic acetal = aq. acid.
Qu55: B
Le Chatilier's principle - shift the equilibrium by removing the
by-product. C is incorrect,
it's equilibrium (reaction requires heat). D is wrong, check the oxidation
states and E is wrong as there
are no rearrangements.
Qu56: C
Looking at an SN1 type reaction, so look at factors affecting the
carbocation intermediate, build a model if needed. A isn't true, the alkyl groups would
stabilise the carbocation. B
isn't correct..... sterics is important in SN2, but in SN1 once the Br
has left, the one face of the carbocation would be very
accessible. D is wrong
! SN2 are fastest for methyl and primary due to low steric
hindrance. E although
water is a weak Nu, the rate determining step of an SN1 is the
carbocation formation.
Qu57: E
Cyclopentadiene is non-aromatic so A
and C are wrong. B is true, but fails to
explain the pKa difference. D
the anion of cyclopentane is non-aromatic.