CHEM212 Summer 2016 Practice Problems 3.

(1) Starting with bromobenzene, propose efficient synthetic routes to the following molecules.
Assume you have access to any other organic or inorganic reagents you may need. In all cases,
since you are starting with bromobenzene, the first step will be to make an appropriate
organometallic reagent, such as a Grignard or Gilman reagent. The way to approach problems
such as this is to recognize the attachment point for the organometallic reagent and to
disconnect at that point. In many cases, this will lead you to the appropriate other fragment
that will be needed. In other cases, you may need to recognize that the TM is derived from the
product of a reaction of the organometallic.

OH
(a
)

(b
) OH

O
(c
)

OH
(d
)

(e OH
)

(f)
 O

(g
)

(3) Identify the products from the following reactions.

(a (b O
Br2
) )
FeBr3 Cl

AlCl3

(c (d
) HNO3 )
Cl
H2SO4
AlCl3

(e (f)
) Cl2 SO3

FeCl3 O 2N H2SO4

O (h
(g Cl2 ) KMnO4
)
FeCl3 H2O

(i)
HNO3
H3CO
H2SO4

(4) Provide products for the following reaction sequences. Note that for the pairs (a) & (b), and
(c) & (d) use the same reagents, but the orders in which they are used are different.
(a) Cl KMnO4 Br2

AlCl3 H2 O FeBr3

(b) Cl Br2 KMnO4

AlCl3 FeBr3 H2O

(c) Cl HNO3 NH2NH2

AlCl3 H2SO4 OH-

O
(d)
Cl NH2NH2 HNO3

AlCl3 OH- H2SO4

(5) Starting with benzene, propose routes to the following molecules. Assume you have access
to any other organic or inorganic reagents you may need.

O
O
(a
(b)
)
Cl

O
Br
(c CO 2H
(d)
)
HN

O Br

(6) The following reaction schemes will not work as written. Identify the problem with the
scheme, and identify the products that would be obtained, if any. Suggest an alternative route
for synthesis of the desired TM.

Br
(a
)
FeBr3
 HNO3 EtBr
(b
) H2SO4 NO 2 FeBr3 NO 2

Cl Cl
(c Cl2 KMnO4
)
FeCl3 AlCl3 H2O COOH

O
O
(c
) Cl Br2 (1) Mg
O OH
AlCl3 FeBr3 (2)

(3) H3O+

(2) Calculate the oxidation levels for each of the compounds (for Tuesdays quiz, be prepared to
show the calculations). The formula is (#C-O bonds + #C-N bonds + #C-Halogen bonds) - #C-H
bonds).

(a) _______ (b) ________ (c) ________ (d) CH3CH2OH ________

(e) CH3CH=O ________ (f) CH3COOH ________ (g) HOCH2CH2OH ________
(h) BrCH2CH2Br ________
(2) Based on the changes in oxidation levels, determine if each of the following reactions is an
oxidation, a reduction, or a non-redox reaction.

(a) ______________________________

(b) ______________________________

(c) The sequence:

______________________________

(d) ______________________________
(e) ______________________________
(f) In (c), what types of reaction are the first and second steps? What reagent(s) would be used
for each?

1st Type: ______________________________ Reagent: _______________________________

2nd Type: ______________________________ Reagent: _______________________________

(3) Predict the products from the following reactions or reaction sequences. Be careful to
consider stereochemistry!
(a)

(b)

(c)

(d)
(3) (supplemental) Worth thinking about for students aiming to really understand.
First a little stereochemistry review what is the stereochemical relationship between the
products from reaction sequences (b) and (c)? Enantiomers, diastereomers or identical?
What would happen if instead of H 2/Lindlaars, I had chosen to pose questions (e) and (f) where
the reducing agent for the first step was Na/NH 3(l) instead? What would be the relationships
between the products b, c, e, and f?
(4) Devise synthetic routes that would allow you to prepare each of the following target
molecules starting from acetylene (ethyne, C 2H2). You may use any other reagents you think are
appropriate. Show both a retrosynthetic analysis and a synthetic scheme. Remember, you are
working backwards from the TM, ultimately needing to start with acetylene itself, so ALL of the
syntheses are going to begin with either one or two alkyne alkylation reactions. Alkylations of
alkenes and alkanes DO NOT WORK in this manner, so if you need to create C-C bonds to get to
the TM, those steps MUST be done before any FGIs on the alkyne.

(a)

(b)
(c)

(d)

(e)

(f)

(g)
(h)

Try to think of some additional target molecules that could be made using the combinations of
the alkylation and C-C bond-forming reactions and FGIs discussed so far. Even though you can
only use methyl and primary R-X compounds in the alkylation reactions, you still have a very
large number of possibilities.