CH 203

Addition to carboncarbon double bonds: Problems

CH3

(1) Predict the organic product(s) of the reaction of isobutylene (at

right) with each of the following reagents. Assume that no carboca-

H3C

tion rearrangements occur.

(a) H2, Pt
(c) HBr
(e) BH3 then H2O2, NaOH, H2O
(g) Cl2, H2O
(i) O3 then Zn, CH3CO2H
(k) Cl2, CH3CH2OH

(b) Br2
(d) H2O, H2SO4, 100 C
(f) FCO3H
(h) OsO4 then NaHSO3
(j) O3 then H2O2

CH3

(2) Predict the organic product(s) of the reaction of 2methylpent-2-ene (at right) with each of the reagents in Prob-

H3C

CH3

lem (1). Indicate which reactions afford a mixture of enantiomers. Assume that no carbocation rearrangements occur.
CH3

(3) Predict the organic product(s) of the reaction of 1methylcyclopentene (at right) with each of the reagents in Problem (1). Clearly show the stereochemistry of the product(s) where appropri-

ate. Indicate which reactions afford a mixture of enantiomers. Assume that no

carbocation rearrangements occur.
(4) Predict the organic product of the reaction of (S)-6methylbicyclo[4.4.0]dec-1-ene (at right) with each of the rea-

CH3

gents in Problem (1). Clearly show the stereochemistry of the

product where appropriate. Assume that no carbocation rearrangements occur.
(5) Hydrogen occurs in the three isotopic forms protium (1H or simply H; this
is plain ol hydrogen), deuterium (2H or D; about 0.05% of all hydrogen atoms
are D atoms) and tritium (3H or T; the only radioactive isotope of hydrogen).
The isotopes differ in the number of neutrons in the nucleus. Except for occasional differences in the rate of reaction, the three hydrogen isotopes react essentially identically. Predict the organic product(s) of the reaction
of 1-methylcyclopentene (see problem (3)) with each of the following deuterium-containing reagents. Clearly show the stereochemistry of the product(s).

Addition to carboncarbon double bonds Problems Bruno I. Rubio

If more than one product results, indicate how each is related to the
other(s).
(a) D2, Pt

(b) DCl

(c) BD3 then H2O2, NaOH, H2O

(6) Predict the products of the reaction of IBr with (S)-6methylbicyclo[4.4.0]dec-1-ene (see Problem (4)), clearly showing the stereochemistry of the product. Write a detailed mechanism of the reaction, using
curved arrows to show the flow of electrons.
(7) Circle the alkenes that are likely to undergo a carbocation rearrangement
upon addition of HCl. In those cases where rearrangement is likely, draw the
structure of the final (rearranged) organic product.
H3C

CH3
H3C

CH3

CH3

CH3

H3C

CH3

(8) Rank these alkenes in order of their rate of reaction with HBr (1 = fastest).

CH3

CH3

CH3

CH3

CH3

OCH3

H3C

CH3

(9) Each of these reactions affords only one of the two products shown below.
Circle the product that forms and explain the reasoning for your selection.

H3C

HCl

H3C

CF3

(b)

HCl
OCH3

Cl
or

Cl

(a)

H3C

CF3

H3C

OCH3
Cl

H3C

CF3
Cl

or

H3C

OCH3

(10) Write detailed electron-pushing mechanisms of these reactions, using

curved arrows to show the flow of electrons.

Addition to carboncarbon double bonds Problems Bruno I. Rubio

H3 C

CH3

Cl
CH3

HCl

(a)

CH3

H3C

HCl

H3C
Cl
CH3

(b)

Br2

+
Br

(c)

CH3

CH3

OH
+

Cl

H2 O

CH3

CH3
HO

CH3

O
+

HCl

CH3

(d)

(e)

HBr

I2

H3C

H3C

HI

The use of hydrogenation and ozonolysis in structure determination

(11) A pine-scented hydrocarbon (C15H24) isolated from a cypress tree reacts
with excess H2 over a Pt catalyst to afford the bicyclic alkane shown below:
CH3

C15H24

excess
H2
Pt

H3C

CH3
CH3

When C15H24 undergoes reaction with excess O3 followed by work-up with zinc
and acid, the following products are obtained:

Addition to carboncarbon double bonds Problems Bruno I. Rubio

CH3
C15H24

(1) excess O3
(2) Zn
CH3CO2H

O
CHO
+

H3C

CH2O

CH3

Suggest a reasonable structure for C15H24.

(12a) Draw six additional, reasonable resonance structures of the molecule at right.

OCH3

(12b) By inspecting the resonance structures you drew,

predict which atoms are likely to undergo attack by a nucleophile.

Addition to carboncarbon double bonds Problems Bruno I. Rubio

ANSWERS

CH3

CH3
(1a)

H3C

Br

CH3

CH3
Br

(1b)

CH3
(1c)

CH3
CH3

H3C

Br

(1d)

CH3

(1e)

OH

CH3
HO

CH3

H3C

CH3
CH3

(1f)

CH3
Cl

CH3
CH3

HO

OH

(1g)

OH

(1h)

CH3

O
+
O

(1i)

CH3

CH3

CH3
(1j)

CH3

CH3
Cl

CH3
OCH2CH3

(1k)

CH3
CH3
(2a)

H3 C

H3C

CH3

CH3

H3C

H3C

CH3

Br

H3C

CH3
OH

H3C

()
(2f)

CH3

HO
(2g)

CH3
CH3

Cl

()

H3C

CH3
H3C

CH3

HO

(2d)

CH3

(2e)

()

Br

(2b)

CH3
(2c)

CH3

Br

H3 C

()

HO
(2h)

Addition to carboncarbon double bonds Problems Bruno I. Rubio

CH3

()

OH

CH3

(2i)

H3C

CH3

CH3

+
H

CH3

+
(2j)

H3C

OH

CH3
H3C
(2k)

()

CH3

CH3CH2O

Cl
CH3
Br

CH3
(3a)

Br

(3b)

CH3

CH3

Br

(3c)

OH

(3d)

CH3

CH3

()

()

OH

(3e)

(3f)

CH3
OH

CH3

H3C

O
H

(3j)

()

OH

(3h)

O
(3i)

OH

()

Cl

(3g)

()

H3C

OH

CH3
OCH2CH3
(3k)

()

Cl
CH3

CH3

(4a)

(4b)

CH3

Br

CH3

Br

CH3

+
(4c)

Br

CH3
+

Br

(4d)

Addition to carboncarbon double bonds Problems Bruno I. Rubio

OH

OH

CH3

OH

(4e)

CH3

(4f)

CH3

Cl

(4g)

CH3

OH
(4h)

CH3

H
O

OH

CH3

HO
O

(4i)

OH

(4j)

CH3

(4k)

OCH2CH3

Cl

CH3

CH3
D
(5a)

CH3
+

Cl

()

(5b)

Cl
D

()

()

CH3
D
(5c)

()

OH

(6) The iodinechlorine bond is polarized away from iodine because iodine is
less electronegative than chlorine. Thus, the iodine end of ICl is partially
positive and undergoes attack the the alkene:

CH3

+
I Cl

CH3

CH3

Cl

Cl
I

Addition to carboncarbon double bonds Problems Bruno I. Rubio

Cl

(7)

H3C CH3

CH3
H3C

CH3

H3C

Cl

CH3

CH3

CH3

Cl

CH3

HCl

HCl

H3 C

CH3

HCl

CH3

CH3

CH3

Cl

(8) The decisive factor is the relative stability of the carbocation formed
when the carboncarbon double bond is protonated by HBr.

CH3

CH3

CH3

CH3

CH3

OCH3

H3C

CH3

(9a)

2
H3C

HCl

H3C

CF3

CF3

Cl
or

Cl

H3C

CF3

The CF3 group is electron-withdrawing by induction and would destabilize a

carbocation at C2; hence, protonation occurs at C2 and the carbocation formed
at C3 is captured by Cl.
(9b)

H3C
2

HCl
OCH3

H3 C

OCH3
Cl

Addition to carboncarbon double bonds Problems Bruno I. Rubio

Cl
or

H3 C

OCH3

The OCH3 group is electron-donating by resonance and stabilizes the carbocation at C1.
(10a)

CH3

Cl

Cl

CH3

CH3

CH3

CH3
=

CH3

CH3

Cl
product
(10b)

H3C

CH3

H3C
H

CH3

H3C

CH3
H3C

Cl
=

Cl

CH3
Cl

product
(10c)
H
H

Br Br

Br

H
Br

Br
=

Br
Br
products

Addition to carboncarbon double bonds Problems Bruno I. Rubio

(10d)

CH3

Cl

CH3

CH3

Cl

CH3

CH3

CH3

CH3
CH3

OH2

H
O
H

CH3

Cl

product

HCl

CH3

(10e)

CH3

CH3 CH3

I I

HO

HO
O

H3C

H
O

CH3

I
product
HI

H3 C

CH3
H3C
(11)

CH3

Addition to carboncarbon double bonds Problems Bruno I. Rubio

10

(12a)

N
OCH3

N
OCH3

OCH3

N
OCH3

C
OCH3

OCH3

OCH3

(12b)
All of the carbon atoms that bear a positive charge may be attacked by a nucleophile. Oxygen, though positive, cannot be attacked by a nucleophile because, if that were to happen, the octet of the oxygen would be exceeded.

Addition to carboncarbon double bonds Problems Bruno I. Rubio

11