Chem 212

Alkyl halide problems 3 Provide the products for the following reactions, show the mechanisms, and all relevant stereochemistry.

HO
NaNH2 +
1. H2O
6. OH
Cl H NH3
Br OH

NaBr NH3
2. 7. Br Br
acetone EtOH
Cl H N
Br H
Br
CN
+ NaCN
3. KOH 8.
DMSO
Cl H

+ OEt Br AgNO3 OEt

4. AgNO3 9.
EtOH
Cl H EtOH OEt

+ I
CsI 10. Br NaCN CN
5.
MeOH DMSO
Cl H I

11. Predict the effect of the changes given below on the rate of the following reaction:
NaCN
Cl MeOH CN

a) change the halogen from Cl to I. faster

b) change solvent from MeOH to DMSO faster

c) change starting material from 1-chloropropane to 2-chloropropaneslower

12. Rank the following sets in order of increasing SN2 reactivity

a) Br Br
CH3Br

fastest slowest
b)
Cl Cl
I
fastest
slowest
c)
Cl Cl Cl

fastest slowest

13. Rank the members of the following groups in order of basicity, nucleophilicity, and leaving group ability.
Expain your answers.
basicity nucleophilicity leaving group ability

a) H2O, - OH, CH3CO2 - -OH > CH3CO2 - > H2O -OH > CH3CO2 - > H2O H2O > CH3CH2CO2- > -OH

I- > Br- > Cl- >F-

b) Br -, Cl -, F -, I - F- > Cl- > Br- > I- I- > Br- > Cl- >F-

- NH > - PH > NH - PH > - NH > NH

c) - NH2, NH3, - PH2 2 2 3 2 2 3 NH3 > -PH2 > -NH2

d) H2O, H2S, NH3 NH3 > H2O > H2S H2S > NH3 > H2O H2S > H2O > NH3

-SMe
e) NaF, NaOH, NaSMe NaOH > NaSMe > NaF NaSMe > NaOH > NaF > -OH > F-