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
reactivity of carbonyl groups towards Grignard
reagents, looking at the relative
reactivity of i esters,
ii aldehydes,
and iii ketones.
Electronic
and steric factors need to be considered. First compare ii and iii, aldehydes
tend to be more reactive than ketones because (1) they are less
hindered and (2) alkyl groups are weak electron donors. Both factors
make the carbonyl C less electrophilic and more hindered
hence less reactive. In esters,
the RO- group of the carbonyl is a strong electron donor, making them
even less reactive than ketones. So we get ii >
iii
> i.
Qu2: AB
The reaction is electrophilic aromatic substitution, and we need
to
look at the substituent
effects on the aromatic ring. The ketone group in i is connected to the ring at the
carbonyl carbon : this C has positive character due to the
electronegative O and there is resonance withdrawal by the C=O group -
it's a deactivating group. The alkyl group in ii is a weakly activating group due
to an inductive effect. The -OC(=O)CH3 group
in iii 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. So the reactivity
is iii > ii > i.
Qu3:C
Acidity...
if you know your pKa's then this is easy : ketone
enolate = 20, carboxylic
acid = 5 and ester
enolate = 25. Remember the lower the pKa the stronger the
acid, so ii > i > 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-.....Note that all the acidic H
are alpha to one carbonyl group. Now look at the atom the H is attached
to. In i and iii it's C and ii it's O. Recall, that C is less
electronegative than O so C is
less stable as an anion compared to O, hence the carboxylic acid is
more acidic
than the ketone or the ester. In the ester the RO- group has lone
pairs on the O that can be donated via resonance to the C=O. This
competes against the donation from the C lone pair in the enolate
making the ester enolate less stable so the ester is less acidic.
Qu4: D
The factors involved here are aromaticity
in ii and iii and ring
strain in i. Cubane, i, has 6 cyclobutane rings.... lots
of ring strain... this makes is unstable. Styrene (aka
ethyenylbenzene), ii, is a
conjugated aromatic system.... this makes it quite stabel.
Cycloctatetraene iii is non-aromatic
= "typical stability". Therefore
ii > iii > i.
Qu5: A
Electrophilic
addition to C=C in a series of substituted alkenes with aq.
sulfuric acid = hydration
reaction . The reaction is controlled by the stability
of the carbocations formed by the addition of the H+ to the
C=C. System i gives a
secondary 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 vinyl
carbocation - vinyl cations are quite difficult to form. Remember
that the
more stable cation is the easiest / fastest
to form, so i > ii > iii.
Qu6: B
Basicity
of substituted aromatic amines means look at the substituent
effects on the aromatic ring. An electron donating group on
the ring will make the lone pair on the N more available, so making the
amine more basic. The methoxy group, CH3O- in i is a strong electron donor, the
Cl- in ii is slightly electron
withdrawing and the H- in iii
is the "reference" - i.e. no effect. Therefore in terms of
basicity, i > iii > ii.
Qu7:AB
Catalytic hydrogenation is easier the weaker the pi bond. This
means alkynes reduce more readily than alkenes and that carbonyl groups
are difficult to reduce in this way (least reactive)..... iii > ii > i.
Qu8: A
Enolisable
H are adjacent to carbonyl groups. In i there are two (one each side), ii has one (on the left, also
adjacent to the methyl group) and iii
has none. So i > ii > iii.
Qu9: E
The reaction is electrophilic
aromatic substitution, a nitration,
we need to consider the directing
effects of the substituents. The Cl is ortho-/ para- directing.
The C=O system is deactivating and
meta- directing. Alkyl groups are ortho-/ para- directing and the
steric effects of the larger tBu group make it favour para over
ortho. So iii > i > ii
Qu11: E
The Lucas test is for alcohols that undergo SN1 reactions. Only the IR
spectra A, D, E
and AB show -OH
groups. D is an aromatic
alcohol (phenol) which don't react in the Lucas test and AB H-NMR suggests a carboxylic
acid. The spectra of E
suggests it's benzyl alcohol, C6H5CH2OH which reacts rapidly under SN1
due to the favourable carbocation intermediate.
Qu12: C
The DNP test gives an orange precipitate with aldehydes and
ketones. Only the IR spectra C
and AB show C=O groups.
The spectra of AB suggest a
carboxylic acid (e.g. IR has an -OH and H-NMR peak at 12ppm).
Qu13: D
The ferric chloride test is for phenols. Only the IR
spectra A, D, E
and AB show -OH
groups. Of these only D and AB have aromatic H in the H-NMR. D is the aromatic alcohol (phenol),
the spectra of AB suggest a
carboxylic acid (e.g. IR has an -OH and H-NMR peak at 12ppm).
Qu14: A
Need an alcohol
that can dehydrate to give an alkene. Only the IR spectra A, D,
E and AB show -OH groups. D is an aromatic alcohol (phenol)
which don't react in the Lucas test and AB H-NMR suggests a carboxylic
acid. The spectra of E
suggests it's benzyl alcohol, C6H5CH2OH which reacts rapidly under SN1
due to the favourable carbocation intermediate. A is cyclohexanol which can
eliminate to give cyclohexene.
Qu15: AB
The DNP test gives an orange precipitate with aldehydes and
ketones. Only the IR spectra C
and AB show C=O groups.
The spectra of AB suggest a
carboxylic acid (e.g. IR has an -OH and H-NMR peak at 12ppm) which
would not react with DNP.
Qu16: B
Alkenes react with bromine in chloroform. The C=C of an alkene can be
seen in the IR of B near
1600cm-1 and the peaks in the H-NMR near 5.6ppm.
Qu17: AC
Basic compounds like amines dissolve in 10% HCl. The IR of AC suggests an NH2 (near 3400cm-1).
Qu18: D
The tests indicate we need a moderate acid... a phenol not a carboxylic
acid. Only the IR spectra A,
D, E and AB show -OH groups. D is an aromatic alcohol (phenol)
which don't react in the Lucas test and AB H-NMR suggests a carboxylic acid.
Set 1 : Assign the configurations to A-E. A = RS, B =SS, C = RR, D = RS and E = RS (note the different alkyl group in E compared to the rest).
Qu19: AD
Meso compounds require RS where the two chirality centers have
the same set of 4 groups attached.
Qu20: BC
Enantiomers
are non-superimposable mirror images - they have the opposite
configurations at chirality centers.
Qu21: AB
or AC or BD or CD
Diastereomers are stereoisomers that are not enantiomers
- the configuration at least one but not all centers are the same.
Qu22: B
Set 2: All about the reactivity of carbonyl compounds, ketones and esters.
Qu23: B
The most reactive of these ketones is the ring strained
cyclopropanone.
Qu30: E
Step 1 is LDA,
a strong base... this will create the carboanion adjacent to the
nitrile group (compare with a C=O), it's a type of enoalte really. Step
2 will add a methyl group via an SN2 reaction of the carboanion (it's
an enolate
alkylation) then step 3 will hydrolyse
the nitrile via the amide to the carboxylic acid.
Qu31: D
Step 1, the 1,3-diol is used to convert the aldehyde to a cyclic
acetal. Step 2... the SN2 reaction of the acetylide
anion on the alkyl bromide. Step 3 reduces
the alkyne to the cis-alkene. Step 4 converts the alkene
to the epoxide where the expoxide has the same stereochemistry as the alkene.
B and C have the wrong stereochemistry. A and B
have one too few carbons in the cyclic acetal.
Qu32: C
Step 1 is the radical
halogenation of the cyclohexane to give bromocyclohexane. Step 2 -
SN2 with the PPh3 then the strong base forms the ylid ready for the Wittig
reaction in step 3 with the ketone to give the alkene. A and B have the wrong alkene.
Qu33: E
Step 1 is the electrophilic
aromatic substitution, in this case chlorination
and so it adds a Cl to a benzene ring - in this case it will add mainly
para to the large aryl group
in the ring without the nitro group since the nitro
group deactivates the ring it is attached to. Step 2 is a Friedel-Crafts
alkylation, this will also occur on the more activated
ring, ortho to the aryl
group. A has the wrong
regiochemistry as both the Cl and the methyl have added meta. B-D neither of the substitutions
occur on the deactivated ring.
Qu34: D
Step 1 is the dissolving
metal reduction of the alkyne to the trans-alkene. Step 2 converts
the alkene
to the epoxide where the expoxide has the same stereochemistry as
the alkene. (i.e. trans). Step
3 - the Grignard
reagent opens the epoxide in an SN2
type fashion (least hindered end attacked).
Qu35: B
Step 1 is the electrophilic
aromatic substitution, in this case bromination
and so it adds a Br to a benzene ring para to the large t-butyl group.
In step 2, the aromatic bromide is converted to the Grignard
reagent then in step 3, this is added to the methanal
to give a primary alcohol. Finally, step 4, a controlled oxidation
by PCC to give the aldehyde. A
has too many carbon atoms in the aldehyde substitutent (we only added
one C), C has too few carbon
atoms and is a ketone. D is
the alcohol obtained after step 3. E ... PCC is not a strong enough
oxidant to form this product.
Qu36: D
The starting material is a lactone... a cyclic ester. In step 1 the
excess Grignard
reagent will react with the ester
to add two methyl groups giving after step 2, the work-up, a tertiary
alcohol from the original carbonyl and a primary alcohol from the
cleavage of the ester. In step 3, an SN2 reaction will convert
the alcohols
to alkyl bromides and then step 4 is the E2
elimination
to give the alkenes in this case a diene and in accord with Zaitsev's
rule. Only D and E are dienes, E has the wrong
regiochemistry.
Qu37: B
The product is an ester - these are typically formed from
carboxylic acids and alcohols with an acid catalyst. The alcohol
could come from the reduction
of a ketone (since it would be a secondary alcohol). The
first step is ozonolysis
with an oxidative work up ... this accounts for the formation of the
carboxylic acid and the ketone from an alkene .... need to get the
alkene in the right place and need a system with 6 carbon atoms.
Only B has the right number
of C atoms and gives a keto-acid after ozonolysis.
Qu38: D
The product is 1,3,5-tribromobenzene. A quick glance at the
reactions suggests we are looking at diazonium
chemistry to remove an amine group. So the first step in the
formation of the amine by reduction
of a nitro group. Aniline is very activated and reacts with
bromine to give the 2,4,6-tribromoaniline.
Qu39: A
PDC
is used to oxidise alcohols, usually to aldehydes or ketones.
Here the product is an aldehyde (remember tertiary alcohols don't
oxidise easily). THe only system that could react to give a
tertiary alcohol here is A by hydration
of the alkene. The first step would reduce
the ester to the primary alcohol. Neither B nor C with undergo hydration to give a
tertiary alcohol and D and E will be reduced by LiAlH4 to give
diols (one secondary -OH and one primary -OH).
Qu40: D
The product is a conjugated enone, a typical aldol
product.... the last two reaction steps are consistent with that...
in this case it's an intramolecular
aldol of 5-oxohexanal... disconnect the enone to reveal the
carbonyl groups and then reconnect to see which alkene
needed to be ozonised (reductive work-up, step 1).
Qu41: B
The product is a highly substituted cycloehexane with specific
stereochemistry. This suggests a Diels-Alder
reaction. Step 2 would convert an alkene
into a 1,2-diol with cis stereochemistry - this information can be
used to "reveal" the alkene. Reverse the Diels-Alder to reveal the
required diene, 2,4-hexadiene. The opposite stereochemistry of the
methyl groups in the product shows the stereochemistry required of the
methyl groups in the diene - only B
has the right stereochemistry (one cis and one trans).
Qu42: D
The product is an aromatic dicarboxylic acid... step 2 in the
reactions suggests that the acid groups have been formed by the oxidation
of aromatic alkyl group. Step 1 is a Friedel-Crafts
alkylation, these only work on activated aromatics - A, C
and E are deactivated
aromatics so no reaction. B has
a t-butyl group which does not oxidise to a carboxylic acid (it doesn't
have a benzylic H).
Qu43: A
Straight from the midterm. 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. D and E would give
2-ethyl-1-butanol. C would give 3-methyl-1-pentanol. B
has
the wrong stereochemistry.
Qu44: ABD
Need to add a t-buytl group via a Friedel-Crafts
alkylation type reaction, here the t-butyl carbocation is formed by
the reaction of the alcohol with the acid catalyst.
Qu45: AE
Now need to add a methyl group via a Friedel-Crafts
alkylation reaction using RCl and AlCl3.
Qu46: CD
Radical
chlorination of the benzylic
methyl group via a stable benzylic radical.
Qu47: B
Alkylation
of the enolate of an active
methylene needs a base
to prepare the enolate.
Qu48: A
Hydrolysis
of the diester and loss of one acid group via decarboxylation
- requires aq. base and heat (see section directions... heat can be
assumed if needed).
Qu49: D
Convert the carboxylic
acid to the ester : typical reaction is ROH plus an acid catalyst.
Qu50: BD
Convert the ethyl
ester into a tertiary alcohol with two new methyl groups by using
an organometallic reagent such as a methyl Grignard.
Qu51: AC
A little more difficult... an intramolecular alkylation... a Friedel-Crafts
alkylation type reaction, here the t-butyl carbocation is formed by
the reaction of the alcohol with the acid catalyst., here the
carbocation is formed by the reaction of the alcohol with the acid
catalyst.
Qu52: BC
And finally we need to add an acyl group via a Friedel-Crafts
acylation type reaction, RCOCl plus AlCl3.
Qu53: D
Hydroboration
/ oxidation of alkenes. The reaction is concerted (no carbocation,
carbanion or radical intermediate), where the B is the electrophilic
atom.
Qu55: C
Addition
of HBr to alkynes... during the addtion of the second equivalent of
HBr, the lone pairs on the Br already added helps stabilise the
developing cation by resonance.
Qu56: B
Resonance of the N lone pairs of Nb and Nc with the adjacent C=O make
them less nucleophilic.
Qu57: C
In this case, the enol is aromatic and hence very favourable.