Practice

 Exam  Packet  for  Dr.  Hoeger’s  Organic  Chemistry  

 
Attached  to  this  cover  sheet  are  a  number  of  items:  
 
1. General  Study  Questions  (i.e.  old  exam  questions;  they  give  you  a  good  idea  of  
what  I  like  to  ask;  
2. Practice  Exams  for  an  entire  YEAR  of  Organic  Chem,  broken  up  by  semester  
(these  are  ACTUAL  exams  that  were  given).  
 
Because  of  changes  in  textbooks  used,  changes  in  coverage,  school  differences,  etc  
you  must  keep  this  in  mind  at  ALL  TIMES:  these  are  meant  to  be  REPRESENTATIVE  
of  past  exams  and,  depending  on  the  school  you  are  at  or  the  quarter  or  semester  
you  are  in  you  may  or  may  not  know  how  to  do  a  particular  problem.  Always  use  
your  homework  and  lecture  notes  s  a  guide.  
 
IMPORTANT  NOTE  1:  NO  ANSWERS  TO  THE  QUESTIONS  INCLUDED  HEREIN  WILL  
BE  PROVIDED  (so  don’t  ask).  You  want  to  know  how  to  do  something,  come  and  see  
me  or  a  TA.  
 
IMPORTANT  NOTE  2:  these  exams  are  light  on  NMR  and  structural  determination.  
Do  NOT  take  this  to  mean  that  you  will  not  see  it!  It  just  so  happens  that  coverage  of  
NMR  was  done  in  a  different  setting  when  these  exams  were  administered.    You  can  
BET  that  if  we  covered  it  in  lecture,  and  homework  was  assigned,  it  WILL  be  covered  
on  an  exam.  
 
FINALLY:  No  practice  final  exams  have  been  included.  Nor  will  any.  They  just  look  
like  long  exams.  
 
Good  luck,  and  remember:  ALWAYS  RELY  ON  FIRST  PRINCIPLES  FOR  PROBLEMS  
YOU  ARE  UNSURE  OF!  
 
SEMESTER  1  BASIC  STUDY  QUESTIONS  
 
 EX AM 1 QUES TIONS
1. Consider the molecule diazomethane (CH2 N2) for which the sigma ( ) network is shown
below. Complete the structure, drawing in all remaining bonds, lone pairs and formal
charges found on the atoms (Hint: the net charge on diazomethane is zero).
H
C N N

2. a) Draw all isomers having the molecular formula C6H14 . Name them.
b) Which one of these isomers will give two (and only two) monochloro products upon
free radical chlorination? Draw these monochloro products and name one of them.

3. Consider the following equlibrium:

H 3C D

H H
D Keq=17.336
H 3C
at 23°C
H H
Given that AMe=1.70 kcal, calculate the A value for a deuterium (NOTE: Be careful about
rounding off!).

4) Compare and contrast reac t ivity and se le ctiv ity in terms of energy and stabilities.
Use examples!

5) Consider the molecule diisopropylcarbodiimide (I ) and its reaction with the anion of
acetic acid(II ):

Using bond polarity, electronegativity, partial charges, etc. predict where II will react with I
and attempt to draw the product. For full credit show your work.
6. Provide a mechanism for the free-radical bromination of 2,2-dimethylpropane.
7. Calculate the relative percentages of 1°, 2°, and 3° monochloro products one would get
from the free radical chlorination of 1-methylcyclohexane. Show your work.
8. How does one use pKa values to predict whether a reaction will occur?
9) Consider the molecular formula C4H 8O. Draw, but do not name, an isomer that is:
i) a ketone
ii) an aldehyde
iii) an alcohol
iv) an ether
10. a) What is meant by torsional energy? b) What factors account for ring strain in cyclic
molecules? c) Why are the A values for methyl (1.7 kcal), ethyl (1.75 kcal) and isopropyl
(2.15 kcal) similar, while that for tert-butyl is so much larger (>4 kcal)?
11) An O’Chem student from Mesa needed a quantity of 4-amino-1-butanol (A) and decided
to make it as outlined below. However, the only product he obtained was compound B .
Explain what must have happened and postulate a mechanism for this process.

NH2
Br-CH2 CH2CH2CH2 -OH H2N-CH2 CH2CH2CH2 -OH
A

CH2 CH2
NH2
CH2 CH2
O
B

12. Calculate the formal charges and/or hybridizations for the indicated atoms:
F
H2C B
F
CH

HC CH2 CH CH2 N C

13. Name the indicated functional groups:

O

O O OH
O Ph O

Ph N O
H
OH O
H
OH O O

O
Ph O

14. Given the molecular formula C7H14:

a) Draw any four non-cyclic isomers.
b) Draw and name any four non-alkene isomers.
15. In conformational analysis of cycloalkanes, the tert-butyl group is used quite frequently as a
'conformational lock'. Consider both cis 1-methyl-4-t-butylcyclohexane and trans 1-methyl-4-t-
butylcyclohexane.
a) Draw the conformational equlibrium for both.
b) Calculate the equlibrium constant (Keq) at 23˚C for both equlibria shown in a). SHOW ALL
WORK FOR FULL CREDIT! Note: AMe=1.7 and AtBu=4.0.
c) For the cis compound, calculate the relative percentages of each conformer at equlibrium.
16. cis 3-Amino-1-cyclohexanol has a high propensity to exist in a diaxial orientation in aprotic
solvents and in a diequitorial orientation in protic solvents. Explain.
17. Draw all the mono-bromo products formed when 2-methylbutane reacts with Br2 in the presence
of light. Name any three.
18. Draw the following structures:
a) 5-chloro-7-ethyl-5-iodo-3-isopropyl-6-methyldecane
b) trans 1-methyl-3-secbutylcyclohexane
c) 1-cyclobutyl-2-cyclopropyl-3-methylcyclopentane
d) 2-isopropyl-3-methyl-1-cyclohexanol (draw in chair conformation with methyl and isopropyl
axial and hydroxyl equitorial)
e) What is wrong with the name 3-iodo-5-isopropylhexane?
19. a) Describe in detail (using examples) how pKa is used to predict whether a reaction will go or
not. Use appropriate labels, distinctions, etc.
b) Explain why CH3CH2- is more basic than CH3CH2O- ("because of pKa" is not an appropriate
answer)
c) CH3CH2O- is much more basic than CH3CO-, although simple principles would not predict this.
Explain.
20. Complete and then predict the outcomes of the following reactions using any principles you
want. NR=No Reaction

a) CH3CH2S + CH3CH2Br

O O

b) C C + CH3Li
H3C CH2 CH3

c) CH3CH2OCH 2 + BrCH2 C CH

C + CH3MgBr
d)
CH3 CH3

21. Starting from any organic starting materials you want of three carbons or less, prepare 2,5-
dimethylhexane.
 ANS WE RS TO E X AM 1 S TUD Y QUES TI ONS
1.
A: There are two possibilities:
H H

C N N or C N N

H H
-
First-count total # of valence e there should be (16; 4 for C, 5 for each N, 1 for each H).
Second, count how many e- are accounted for with the structure (8; for bonds at 2 e- each).
Finally, fill out structure with remaining e-’s.

2.
A: C6 H14-no double bonds or rings
a)

hexane 3-methylpentane 2,2-dimethylbutane

2-methylpentane 2,3-dimethylbutane

b) 2,3-Dimethylbutane is the only one that will give only two products because it is the only
one with ONLY 2 different types of hydrogens (all others have 3 or more different types of
hydrogens). The products one would get are:
Cl
Cl
and

3.
H 3C D

H H
D Keq=17.336
H 3C at 23°C
I H H II
A: As the equlibrium is defined, methyl is going from axial to equitorial, and deuterium is going
from eq. to ax. Therefore AT = AMe + [-AD] = RTlnKeq ; substituting in numbers, we get: 1.70 -
AD = (1.986 x 10-3)(300)(ln 17.336). Simplifying we get -AD = 1.6996895 - 1.70 or AD=3.104 x
10-4. As one might predict, the A value for D is very small, as expected.

4)
A. Reactivity and selectivity are inversely proportional; as a species has higher E, it is more
reactive (remember everything is trying to get to lower E). As reactivity increases, selectivity
decreases (no time to be ‘picky’). Best example is Cl• vs. Br• . See lecture discussion for more
details.
5)
A:
O

d d d
N C N O CH3

II will react at central carbon of I; product should look like:

N C N

O O

CH3

6.
A. 2,2-Dimethylpropane [(CH3 )4C] has only one type of hydrogen (1°). The mechanism is as
follows:
Br2 — 2Br• (Initiation; done with light {h })
(CH3 )3C-CH3 + Br• — (CH3 )3C-CH2• + HBr (First propagation step)
(CH3 )3C-CH2• + Br2 — (CH3 )3C-CH2Br + Br• (Second propagation step)
Chain termination steps need to be shown as well (see notes and book)

7.
A: 1-Methylcyclohexane has three 1°, ten 2° and one 3° hydrogen(s). Using a Cl• selectivity ratio
of 1 : 3.6 : 5 and multiplying the number of a given type of hydrogen by its’ selectivity, one
obtains the following sets of numbers:
1° pdt:2° pdt:3° pdt is (3 x 1):(10 x 3.6):(1 x 5) = 3:36:5.
Therefore the relative percentages are 6.8% 1° product, 81.8% 2° product and 11.4% 3° product.

8.
A: Compare the pKa value of the acid with the conjugate acid that is derived from the base
used; if going from a strong acid to a weaker acid the reaction will go (i.e. equlibrium will lie on
the right). If you find you are going from a weak acid to a stronger acid the reaction will NOT
go (i.e. equlibrium will lie on the left).
9)
A:
O
i) Ketone

O O
ii) Aldehyde
H
or
H

iii) Alcohol (there are MANY possibilities)

OH OH
OH OH etc.

iv) Ether (there are MANY possibilities)

O
O
O etc.

10)
A: a) Torsional energy is the E required to move one group past another while rotating around a
carbon-carbon single bond; in a general sense it is the energy necessary for two groups to be in
close proximal space to one another (later we will refer to this as st eric s tra in or s t eric
hinder ence ). Torsional energy is derived from van der Waals repulsions, etc.
b) Ring strain = Torsional strain + angle strain. The torsional energy in rings comes from
eclipsing interactions while angle strain comes from trying to put a bond angle of 109.5° into a
limited, smaller space.
c) t-Butyl is the only one that can’t ‘hide’ the branching methyl group:
H
H H H
H H C CH3
C H H
H
vs. vs.

CH3 CH3
H H H CH3
C CH3 C CH3
H H

vs.
11)
A: This is a pKa problem, first and simply!

Br-CH2 CH2 CH2 CH2 -OH + NH2 Br-CH2 CH2 CH2 CH2 -O + NH3

pKa ! 16 pKa ! 33
Strong to weak; therefore this reaction will go! (Equlibrium will lie FAR on the right). After this
reaction occurs, an internal substitution reaction occurs that leads to the final product:

Br-CH2 CH2 CH2 CH2 -O

12
A: Remembering that formal charge = group # of atom - [0.5 x # of shared e-] - [# of unshared e-], we
get the following results:

F
H2C B
F
CH

HC CH2 CH CH2 N C

13)
A: Here are all the functional groups:

O O OH
O Ph O

Ph N O
H
OH O
H
OH O O

O
Ph O
14)
A: This problem is similar to #2 and #9 above. The answers in a) can not have rings, while the answers
in b) can not have double bonds.

15)
A: a) The conformational equlibrium for both is as follows:
CH3
CH3 H3C C CH3
H3C
H3C C H H CH3
Cis compound
H3C H
I II H

CH3
H H3C
C CH3
H3C
H3C C CH3 H Trans compound
H
H3C H
III IV CH3

b) As the equlibria above are defined, for the Cis compound methyl is going from axial to
equitorial and t-butyl is going from eq. to ax; for the Trans compound both methyl and t-butyl
are going from eq. to ax. Therefore, for the Cis compound, ATcis = AMe + [-AtBu] = -2.3; for the
Trans compound, ATtrans = [-AMe] + [-AtBu] = -5.7. Using 23°C (296°K) and substituting
numbers into AT = RTlnKeq, we get: Keq(cis) = 2.0 x 10-2 and Keq(trans) = 6.15 x 10-5 .

c) Using Keq(cis) = [II]/[I] = 2.0 x 10-2 we get [I I] = 0.02[I] or [I] = 50[II]. Based on these ratios
we get relative percentages of 98% of I and 2% of I I at equlibrium.

16)
A: In aprotic solvents cis 3-Amino-1-cyclohexanol will undergo internal hydrogen bonding; in protic
solvents, it will hydrogen bond with the solvent making the group much bulkier and thus less likely to
be axial:
ROH HOR
H
HN OH
vs. NH2 OH HOR
H ROH
H
H H
HOR
ROH

17)
A:
 Br
Br
Br
1-bromo-2-methylbutane 1-bromo-3-methylbutane
Br
2-bromo-3-methylbutane or
2-bromo-2-methylbutane 3-bromo-2-methylbutane
18)
A: a) thru d)--Come on, you can do these!
e) If you draw the structure and count the longest chain in what you drew, you will find it is 7 not 6!

19)
A: a) See Q # 8 above. b) Oxygen is more electronegative than carbon and as such can support (and
therefore stabilize) a negative charge better. c) The second compound can stabilize the negative charge
through resonance while the first one can not (dispersal of charge):

O O

H3 C O H3 C O

(Yes, I did have a misprint in the set of questions I gave you...sorry!)

20)
A: Here are the answers; the principles used to solve them are as follows: a) bond polarity/partial
charge; b) pKa; c) pKa; and d) bond polarity/partial charge:
a) CH3CH2S + CH3CH2Br CH3CH2-S-CH 2CH3 + Br

O O O O
Li
b) C C + CH3Li C C + CH4
H3C CH2 CH3 H3C CH CH3

c) CH3CH2OCH 2 + BrCH2 C CH CH3CH2OCH 3 + BrCH2 C C

O O MgBr

C + CH3MgBr C
d) CH3 CH3 CH3 CH3
CH3

21)
A: We will do this in class...
SEMESTER  1  EXAM  1  QUESTIONS  
 
1.(15 pts) a. Calculate the formal charge for the indicated atoms; put answer next to arrow. Show work for the two atoms
in II in space below (no others). NOTE: All lone pairs are shown if present, except forFl which has an octet!

C O O O
I) III)
II)
C F3B C CH2
CH3 CH OCH3
N

H
O

b. Fill in the blanks:

The compound in I) has _____ sp3 carbons and _____ sp2 carbons; The compound in II) has _____ sp3 carbons, _____

sp2 carbons, and _____ sp carbons.

Compound I has how many H’s that are NOT shown?_______
The compound with the LEAST primary hydrogens is _______

2) (8 pts) Provide names for the following:

F
I
Cl
3) (10 pts) Draw all resonance structures possible for the anion shown below:

O N N
CH3
4) (5 pts) Cipro® (Ciprofloxacin) is a synthetic broad spectrum antibacterial agent. It was most recently in the news as the
antibiotic of choice for the treatment of anthrax. The structure of Cipro is shown below. Circle and identify as many
functional groups in the Cipro representation below as you can.

5). (20 pts) Consider the molecule 1-iodo-2-chloropropane with respect to rotations about C1-C2. Given the torsional
energy values below, answer the following questions, putting your answers on the next page.
a) Draw the line-angle structure of this molecule:
b) Draw the THREE MOST stable conformations expected for this molecule using Newman projections looking
down the C1-C2 bond (for all htree conformations keep the CH3 on carbon 3 ‘up’); Rank then from MOST
stable (I) to LEAST (III).
c) Draw the LEAST stable possible conformation expected for this molcule using a Newman projection (HINT:
NOT one of the ones you drew in (b)).
d) Calculate the equlibrium constant at 27°C for the following interconversion:

MOST Stable Rotomer (I) !!

# !
" LEAST Stable Rotomer (III)
!
e) Calculate the relative percentages of the two conformers at equlibrium

Note that the values given are estimates of the per interaction energy cost; if a value is not given, assume it is ≈0.

Gauche E per Eclipsed E per

Interaction interaction Interaction interaction
(kJ/mol) (kJ/mol)
Cl/H 0.84 Cl /H 4.18
H/H 0 H/H 4.18
CH3/I 5.85 CH3/I 9.20
I/H 4.18 I/H 1.67
Cl /I 5.10 Cl /I 5.10
CH3/H 1.67 CH3/H 7.53
6). (25 pts) a) Using pKa data, calculate equilibrium constants for the following reaction (note: you may have to estimate
pKa values from your table!)
i)
O O

+ CH3CH2O-
+ CH3CH2OH

ii)

- O-
OH + OH + H2O

iii) for ii, calculate the relative percentages of OH– and (CH3)3CO–.
iv) Anion A is much more stable than anion B. Explain.

O O O O

A B

v) Explain the leveling effect; using your explanation, tell why NaNH2 can not be used in ethanol (CH3CH2OH).
6). (20 pts) a) Consider the following IR information for the reaction sequence provided. Use this to identify each material
in the reaction:
Compound A is treated with LiAlH4 to give compound B, which upon heating in the presence of acid is converted
to compound C. Compound C reacts with HBr to give compound D, which is in turn reacted with Mg metal,
followed by CO2 to give, after a standard work-up, Compound E.
IR Data (only major absorbances given):
Compound A: 2920 cm–1 (s); 1715 cm–1 (s); 725 cm–1 (w);
Compound B: 3450 cm–1 (s, br); 2980 cm–1 (s) 1150 cm–1 (s);
Compound C: 3050 cm–1 (m, sharp); 2950 cm–1 (s) 1620 cm–1 (m, sharp);
Compound D: 2950 cm–1 (s) 620 cm–1 (s);
Compound E: 3200 cm–1 (s, very br); 1705 cm–1 (s); 1190 cm–1 (s);
The “suspects” are below; put the appropriate leter below which compound you think is which:
O
OH Br
OH O
C

b) Interpret the following IR

WHAT LIKELY IS PRESENT WHAT CAN NOT BE PRESENT

SEMESTER  1  EXAM  2  QUESTIONS  
 
Name: _____________________________ Page 2 of 4

1. For the reaction of (S)-2-iodobutane with CN – in acetone, provide the following:

a) product(s) expected; b) rate expression; c) mechanism; d) transition state(s) expected; and e)
reaction coordinate diagram for this reaction if it progresses as an SN 2 reaction. Assume the reaction
is exothermic. Be sure to completely label your reaction coordinate diagram.

2. a) Using transition state drawings discuss how the SN2 and E2 reactions compete and why the
stereochemical outcomes of the products are as observed when (R) 2-iodo-3-methylbutane is reacted
with CH 3O –

b) Briefly, what factors influence SN1 over E1 and vice versa?

3. a) Provide the mechanism for the addition of HI to 1-butene.

b) When HI is added to 3-methyl-1-butene instead of 1-butene, a different product than expected is

obtained. What is this unexpected product and provide a mechanism for its formation.

4. a) State Markovnikov’s rule and give the modern interpretation of it. Illustrate what you describe
using pictures!

b) What is Zaitsev’s rule? Provide an example.

c) What is Bredt’s rule? Provide an example.

5. Provide the stereochemistry for each chiral centerin the molecules below:

CH3

H Cl
OH
Br H
CO2H
H Br

CH3 NH2

Cl

Br

Br (Include the double bond)

Name: _____________________________ Page 3 of 4
6. Provide the expected products for the following reactions. Show Stereochemistry where needed:

HCl

Br2/CCl4

(1) B2H6

(2) H2O2, OH-

(1) O3

(2) Reductive WU

HBr/HOOH

CD3
mCPBA

OsO4

H2O2
Name: _____________________________ Page 4 of 4
SEMESTER  2  EXAM  1  QUESTIONS  
 
1) During a study aimed at exploring the effect of steric hindrance on the
reactivity of para-substituted arenes, a researcher was in need of 4-
neopentyl-1-isopropylbenzene (A). This question deals with aspects of
the synthetic protocols necessary to prepare it from isopropylbenzene.

a) The initial synthetic scheme required 1-bromo-2,2-dimethylpropane, the A

most efficacious synthesis of this being a free-radical bromination of
2,2-dimethylpropane (neopentane).

i) Provide a complete mechanism for the monobromination of neopentane.

ii) What differences would you expect to see in the proton NMR for 1-bromo-2,2-
dimethylpropane versus neopentane? What about the CMR?
 iii) During the purification of the reaction, a small amount (< 1%) of a side product was
isolated (MW < 150). NMR analysis gave a spectrum with singlet resonances at δ 1.21 and
1.06 ppm in a ratio of 1 : 4.5. What is it and how is it formed?

b) Once prepared, 1-bromo-2,2-dimethylpropane was reacted with isopropylbenzene and AlBr3;

however, after work-up of the reaction mixture, NO A was isolated. Instead, a single product (with
a molecular weight identical to that expected for A) was obtained in good yield. NMR analysis
showed (in addition to other expected resonances) the unmistakable presence of an ethyl group.
What is this product and provide a mechanism for its formation.
c) Starting with isopropylbenzene and any other materials you wish, synthesize A (more than one step
will be required).

R1

2. Acyclic dienes of the type shown below are notoriously unreactive in Diels-
Alder reactions, especially with R1 and R2 being C2H5 or larger.
R2
a) Draw and name the diene with R1 and R2 = C2H5 using correct
stereochemical nomenclature.

b) Suggest a reason for the unreactivity of dienes of this particular stereochemistry. BE CLEAR IN
YOUR ANSWER.
3. Conjugated trienes will undergo electrophilic addition reactions to give only 1,2 and 1,6 addition
products when reacted with one equivalent of electrophile. Consider the reaction of 3,4-dimethyl-
1,3,5-hexatriene with one equivalent of HI.
a) Draw and name the two addition products expected to be formed in this reaction (ignore
stereochemistry).

b) Provide a mechanism for the formation of the 1,6 addition product.

c) Which product (1,2 or 1,6) is expected to be the thermodynamic product and which is
expected to be the kinetic product? Briefly explain the concepts of thermodynamic and
kinetic control of a reaction.
d) No 1,4 addition product is seen. Explain why.
4. Briefly, what are the four key pieces of information obtained from an NMR spectrum, and what
does each tell us about the molecule?

5. Provide a possible explanation for the following trend in IR stretching vibrations for C-X bonds:
Fluorides:1400-1000 cm-1; Chlorides: 800-600 cm-1; Bromides: 625-400 cm-1; Iodides: 625-400 cm-
1
6. Provide products for each step in the multi-step syntheses shown below:

a) CH3
1. AlCl3/ HO2 CCH2 CH2COCl
2. Zn(Hg)/HCl; reflux
3. PCl5
4. AlCl3 (dilute conditions)
5. NH2NH2 /KOH/heat
CH3

b)
1. AlCl3 / excess CH3 CH2I
2. KMnO4 / KOH/heat
3. Na metal / NH3 / EtOH
c)
1. H2 SO4 / heat
2. NBS / light
OH 3. EtO-Na+ / EtOH / heat
4. NBS / light

7. Devise a synthesis of ANY TWO of the following molecules, using a Diels-Alder reaction in at least
one of the steps. You will probably need more than one step for at least one of them. You may use
any starting materials you wish; pay attention to final stereochemistry if indicated.

CH3 b) c) O
a) CO2Et
O CN
H
CH 3 CO2Et H
HO
CN

8. Attached are NMR spectra for two compounds, each with the molecular formula C4H8O2.
Interpret each spectra and come up with a possible structure for each. Remember, you will be give
most of your points for your logic and interpretation NOT for the final structure! Integral heights
are provided in mm.
  
SEMESTER  2  EXAM  2  QUESTIONS  
 
1. a) Provide the mechanism for the Wittig reaction between benzyl triphenylphosphonium bromide (I)
and acetaldehyde (II) in the presence of t-BuLi. Provide names of the intermediate species where
appropriate.
O
CH2 PPh3 Br C
CH3 H

I II
b) Show how one might make benzyl triphenylphosphonium bromide (I).

2. The Grignard reaction is a convenient way to make a variety of different products.

a. Consider the reaction of phenyl magnesium bromide with O

diethyl carbonate (III). What product would you expect to
obtain in the presence of an EXCESS of the Grignard CH CH O C OCH2 CH3
reagent? Provide a complete mechanism for its formation. 3 2

III
b. When methyl magnesium bromide reacts with propionitrile (CH3CH2CH2C≡N) one obtains
2-pentanone (DRAW!) after work-up with H+ /H2O. Provide the mechanism for this addition;
be sure to point out why the reaction stops where it does.

O
c. Now consider the reaction of ethyl magnesium bromide
with oxirane IV, followed by treatment with dilute acid H CH2O-tBu
in water. Draw and name (with correct stereochemical
designations!) the product you expect to obtain. H3C CH3

IV
(optically active)
3. Each of the following compounds leads to either an unsuccessful preparation of a Grignard reagent
or an unsuccessful reaction with Grignard reagent. Briefly explain why for each.

Br
OH

O
CH

CN

OTs
I
O-tBu

I
N(Me)3
O

O O
Br
OCH3

4. The following reaction scheme was employed in an attempt to make hexane-1,2,6-triol (TMS =
trimethylsilyl):

OH
H2C
1) NaNH2 1) H2/Ni2B 1) MMPP/EtOH HO
HC CH A B
H+/H OH
2) 2) Bu 4N +F- 2) 2O/50°C

Br
OTMS

a. Draw the structures of A and B.

b. What is the product obtained after the MMPP step?

CH2
c. Upon completion of the reaction none of the triol was obtained; instead, a high
yield of V was obtained. Provide a possible mechanism for its formation.
O

d. 1-trimethylsiloxy-4-bromobutane can be obtained in two steps from tetrahydrofuran. How?

5. Complete the following reaction sequences; provide stereochemical formulas where needed:

1) D PCC
PBr3 Mg/ether
a) Cyclopentanol C E F G
+
2) H /H2O
+
H /Cr2O72-

D
 H2SO4 1) N Na (s)
MCPBA
b) Cyclohexanol H I O P
heat +
2) H /H2O
H+ (dry)
Add M
CH3 OH

HBr (conc) trans-1-cyclohexyl-2-

K L + M methoxycyclohexane
heat
Mg/ether

N
6. Devise a synthesis of each of the following. Unless indicated otherwise, you may use what ever
reagents and/or starting materials you wish:

a) O CH2Ph

b)

OTs
c)

using ONLY
cyclopentene as your
sole carbon source
and employing a
Wittig reaction

d)
using ONLY
cyclopentene as your
sole carbon source
and employing a
Grignard reaction
e)

OH

f)

OCH2 CH3
  
SEMESTER  2  EXAM  3  QUESTIONS  
 
 
Chem 233 Exam 3

Part 1: Transformation Mechanisms.

There are two primary reasons for learning all of the reactions in the detail that we have for this course.
The first reason is synthesis (of course). The second reason we learn so many reactions is as important,
if not more, than synthesis: the “why” certain transformations occur. For the following reactions,
provide a mechanism for their occurance. You will need to rely on all reactions and principles you have
learned in organic chemistry to date to solve these problems.

1.
OH
HN O
COOEt COOEt
Et3 N
+ N

Br

2.
O
O O
NaH

OH
NO2 NO2

3.

CH3 CH2 ONa

SO2 SO2
O NH
CN
O
4.
O CH 3

CH 3O CH3 NH2 N O
OCH 3

O CH2
O
OCH3

5.
O

O O H+
O
+ Acetone

COOH OH

6.
O
COOH
Br
1) NaOH

2) H+

7.
O
O
Cl-CH2 -COOEt

NaOEt COOEt

Part 2: Synthesis
What else can I say?

8. Prepare, using a Robinson Annulation as one of the steps employed in your synthesis:
O

O
9. Prepare
O

Ph Ph

starting from cyclohexanone and anything else you wish.

10. Prepare
O

CN

starting from cyclohexanone and anything else you wish.

11. Design a method to accomplish the following transformation:

O
O

CN

12. Starting with α-bromo ethyl acetate prepare the following lactam.
O

CH 3
N

N
CH3
In this synthesis you must employ both a Reformatsky reaction and a Michael addition (in separate
steps).