Org Chem I

Problem Set Ch 11

1. Show the actual configuration for each of the following products assuming that the
starting material is optically pure (R)-2-iodobutane. Do not worry about any
elimination products. We Will Cover This In CH 17
TosCl

KOH

H I
(R)-2-Iodobutane

H2O

TsO H

HO H
NH3

NH3

O PP O SI TE ST ER EO
CH EM IS TR

H3N H
I

H NH 3
I

2. In the blank on the left show the primary mechanism which would be expected for
each of the following reactions? Chose from SN1, SN2, E1, E2.
S N1 (CH ) CBr +
3 3

H2O

E2 (CH3)3CBr +

KOH

CH 3
3 alkyl halide and
H3C C OH ionizing medium
CH 3
CH 3
3 alkyl halide and
C
H2C
CH 3 strong base
CH 3CH 2CH 2CH 2OH Unhindered primary
always S N2

S N2 CH CH CH CH Br + KOH
3
2
2
2

S N2 CH3CH2CH2CH2Br +

(CH3)3CO +K

CH 3CH 2CH OC(CH 3)3 DITTO

3. To the right, in Question 2 above, show the structure of the product for each
reaction. SEE ABOVE
4. Show the reactants that would be needed for the synthesis of the following
products using a nucleophilic substitution reaction.
CH 3CH 2CH 2-X + OC(CH3)3
CH 3CH 2CH 2-X + SCH3
or
CH 3CH 2CH 2-S + X-CH3
CH 3CH 2CHX 2 + 2 OCH 3

CH3CH2CH2OC(CH3)3 Must use unhindered

substrate
CH2CH3CH3SCH3
O

CH 3

CH3CH2C O CH3

Either way will work

5. What reagents will be needed to synthesize the following products using a

nucleophilic substitution reaction?
CH3

CH3CH2

CH 3CH 2-X + OCH(CH3) 2

Nitrogen anions are very strong

CH3CH2NHCH2CH3 bases but the substrate is
unhindered

CH 3CH 2-X + NHCH 2CH 3

CH3CH2SCH3

CH 3CH 2-X + SCH3

CH 3 C C

Must use unhindered

O CHCH3 substrate

CH3C CCH3 The acetylide anion is a strong

nucleophile (see CH8)

+ CH 3-X

6. Show the stereochemistry of each product in the following synthesis scheme.

WE WILL COVER THIS IN CH 17.
OH CH SO Cl
CH3
3
2
CH3CH2 C
H

CH 3
CH 3CH 2

K
CH 3
CH 3CH 2

OSO 2CH 3 OH
H2O

HOCH3

CH 3
CH 3CH 2

OCH3

NO Reaction

7. In each pair, circle the condition would cause the faster reaction in an SN2
mechanism?
a. DMSO solvent or water solvent
b. 0.1 M nucleophile or 1.0 M nucleophile
c. OH nucleophile or NH2 nucleophile
d. CH3O nucleophile or (CH3)3CO nucleophile
e. I leaving group or CH3SO2O leaving group
f. OH nucleophile or SCH3 nucleophile
g. CH2CH2Br reactant or CH 3CH(Br)CH3 reactant

H
OH

8. Show the complete mechanism for the reaction of the following optically active
compound under the different conditions listed. (Note. The predominant
mechanism is different for each different set of conditions.)
CH3
C3H7

nucleophile

C Cl

H
a.
Nucleophile
Nucleophilic Conc
Solvent Polarity
Temperature
high
medium (alcohol)
high
OH
THE STRONG BASE (HO ), HIGH CONCENTRATION AND HIGH
TEMPERATURE FAVORES THE E2 PROCESS
CH 3

CH 3
C

CH 3CH 2CH
H

Cl + OH

CH 3CH 2CH

CH 3
CH 3CH 2CH C
H

Cl

HO

ZAITSEV
PRODUCT

Transition State

b.
Nucleophile
Nucleophilic Conc
Solvent Polarity
Temperature
high
low (benzene)
warm temp.
OH
SOLVENTS OF LOW POLARITY SUCH AS BENZENE FAVOR SN2 ON
SECONDARY ALKYL HALIDES
CH 3CH 2CH 2 CH 3

CH 3
C

HO + CH 3CH 2CH 2

Cl

HO

CH 3
HO

Cl

H
Transition State

CH 2CH 2CH 3
H

INVERTED
STEREOCHEMISTRY

c.
Nucleophile
Nucleophilic Conc
Solvent Polarity
Temperature
H2O
low
high (water)
room temp.
GOOD IONIZING SOLVENT (H2O) AND LOW NUCLEOPHILE
CONCENTRATION FAVOR THE SN1 PROCESS
CH 3CH 2CH 2 CH 3

CH 3
C

CH 3CH 2CH 2

Cl

H2O

+ Cl

ionizing solvent

H
O

H
H

CH 3

Nucleophilic attack
0n carbocation

CH 3
C

CH 3CH 2CH 2
H

OH 2 + H2O

CH 2CH 2CH 3
H

RACEMIC MIXTURE

-H+

CH 3
C

CH 3CH 2CH 2

OH

+ Other Enantiomer

9. Show the complete mechanism for the reaction of the following optically active
compound under the different conditions listed. (Note. The predominant
mechanism is different for each different set of conditions.)
CH 3CH 2
H

a.

Cl

Cl

Br

SEE MECHANISM IN PROBLEM 8c ABOVE

S N1 Assume water present as an ionizing solvent

CH 3
CH 3CH 2
H

b.

Br
S N2

CH 3

SEE MECHANISM IN PROBLEM 8b ABOVE

10.The following two compounds are both considered strong bases with about the
same basic strength. However, they do not have the same nucleophilic strength.
a. CH3CH2O- b. (CH3)3COb. Which one is the weakest nucleophile, a or b? _B___
c. What reasoning did you use in your choice of the weakest nucleophile?
Anion B is much too hindered to be an effective nucleophile...It has a much
harder time getting at the backside of the carbon-leaving group bond in the
substrate molecule
11.Assume a nucleophilic substitution takes place with a mix of SN1 and S N2
character. Which, of the reagents or conditions, below, would increase the percent
of SN2 character in the reaction?
a. [YOUR ANSWER MUST BE: a, b, or neither .]
b. Nucleophile = (a) H2O, (b) -OH b Nucleophilicity parallels basicity
c. Nucleophile = (a) CH3CH2O-, (b) (CH3)3CO- a It is much less hindered
d. Nucleophile = (a) 1M CH3CH2O-, (b) 0.1M CH3CH2O- a Higher nucleophile
concentration favor Sn2
e. Solvent = (a)

, (b) CH3OH a Non-polar solvents favor SN2,

whereas polar, protic solvents like ROH are ionizing

f. Solvent = (a) H2O; (b) CH3OH b Water is a stronger ionizing ionizing
solvent and will favor SN1 more.
g. CH3 substituted for H
favors SN2

(b) H substituted for CH3 b Less steric hinderance