Chapter 6 Reactions of Haloalkanes: SN2

I. Naming Haloalkanes
A. Treat Halogen as a substituent to an alkane: chlorine = chloro-
B. Name as in alkane nomenclature
F I

Br
Cl
2-bromo-2-methylpropane cis-1-chloro-2-fluoro 4-(1-iodoethyl)heptane
cyclohexane

II. Physical properties of haloalkanes

A. Bond Strength
1) For RCH2X, F > Cl > Br > I bond strength
2) F has best size for overlap
3) Bond Length: I > Br > Cl > F

B. Polarity: Halogens are more electronegative than C, so bonds are polar

1) Polar R-X bond can be attacked by cations or anions
 2) Polarizability = how much the electron cloud is deformed by other
charges, combination of size and charge effects
d+ d-
R X a) I > Br > Cl > F because of larger size and same charge (-1)
d- d+ b) London Forces are largest for Iodoalkanes because of polarizability
X R
c) Boiling points: MeI > MeBr > MeCl > MeF > Methane

II. Nucleophilic Substitution

A. Nucleophile/Electrophile
1) Molecule or Ion with a lone pair of electrons seeks to share or donate their
“extra” electron density to a (+) or (d+) “nucleus”
a) Nucleophile = nucleus (+) loving = Nu
b) Nucleophiles = Lewis Bases

2) Molecule or Ion having (+) or (d+) region seeks extra electron density
a) Electrophile = electron (-) loving
b) Can be a Lewis Acid, but not necessarily
c) Just needs d+, so any polar bond should have one electrophilic area
d) An atom with a full octet can still be an electrophile
+ -
d d
R X
B. Nucleophilic Substitution Reaction
1) - -
Nu + R X Nu R + X
+
Nu + R X Nu R + X-

2) Leaving Group = ion or molecule replaced by Nu (X) “Substitution”

3) Color codes in your book: Nu = red, Electrophile = blue, LG = green
4) Examples

- -
HO + CH3 Cl CH3 OH + Cl

CN- + + I-
I CN

+ -
NH3 + Br NH3 Br

C. Electron Pushing in Mechanisms

1) Move e- from e- rich to e- poor sites
+ -
2) Acid-Base example H2O + HCl H3O + Cl
 a) O lone pair become O—H bond
b) H—Cl bond becomes Cl lone pair
c) Curved arrows show “flow” of the electrons

3) Organic mechanisms, same thing: Must Draw Correct Lewis Structure

a) Nucleophilic Substitution
-
HO + CH3 Cl CH3 OH + Cl-

b) Dissociation
+ -
CH3 I CH3 + I

c) Nucleophilic Addition
O O-

OH
-
+ HO R
R R
R

d) Electrophilic Addition
H
+ +
C C + H
C C
 D. Kinetics tells us about mechanisms of Nucleophilic substitution
1) Nucleophilic substitution is 2nd order process: rate = k[OH-][CH3Cl]

OH
-
+ CH3 Cl CH3 OH + Cl-

a) If double [OH-], double rate

b) If double [CH3Cl], double rate
c) Rate depends on both S.M., they must both be in rate determ. step
2) Bimolecular Process
3) SN2 = Bimolecular Nucleophilic Substitution
a) Concerted: bond-making and bond-breaking happen simultaneously
b) Front-side or Back-side displacement?

Front-side attack Back-side attack

c) For Achiral reactants, products are identical (No Help!)

d) What about for Chiral reactants?

e) SN2 gives Stereospecific Inversion of Stereochemistry
f) SN2 happens exclusively through Back-side attack