Alkyl Halides

Lecture Notes

Alkyl Halides
3

Cl

2 1

4 5

Br
Cl Cl

OH I
Cl

CH 2Cl2

CHCl3

CCl3F

Freon-11

CCl2F 2

Freon-12

Sn aliphatic & Elimination

SN aliphatic & E are competing reactions

Sn aliphatic & Elimination

OCH2CH3 + Na Br Br + CH3CH2O Na
+

+ CH3CH2O H + Na Br

Nucleophilic Aliphatic Substitution

SN1 & SN2 Mechanisms

q q q q q q q

Kinetics Reactivity of the RX Structure of the Nucleophile Leaving Group Stereochemistry Solvent Competing Reaction

SN2 Mechanism

SN2:

Rate of Reaction

SN2:

Nucleophilicity

SN2: Structure of RX

SN2: Structure of RX

SN2: Structure of RX
(Leaving Group)

SN2:

Inversion of Stereocenter

SN2:

Inversion of Stereocenter

SN1 Mechanism

SN1: rate of Reaction

Strength of nucleophile has NO EFFECT
q

SN1: Structure of RX

SN1: Structure of RX

SN1: Structure of RX

SN1: Stereochemistry

Retension & inversion of configuration

SN aliphatic:
q

Effect of Solvent

SN1: PROTIC SOLVENTS - contain OH groups and are Hbond donors - H2O, HCOOH, MeOH, EtOH, HOAc - aid in ionization of C-X bond to give X- & C+

SN aliphatic:
q

Effect of Solvent

SN2: APROTIC SOLVENTS - do not contain OH groups and cannot function as H-bond donors DMSO, Acetone, DCM, Ether - solvate only cations - allow for highly reactive anions as Nu-

SN1 VS SN2

SN1 VS SN2

 - Elimination Reactions

Elimination:

Regioselectivity

Major products in eliminations are the alkenes that are thermodynamically most stable.

E2 Mechanism

E2: rate of reaction

Rate=k[RX][base]

E2: reactivity of RX

E1 Mechanism

E1: rate of reaction

Rate=k[RX]

E1 VS E2
Alkyl halide
Primary

E1
Does not occur (unstable carbocation)

E2
Favored

Secondary & Tertiary

Main reaction with Main reaction with weak bases such strong bases such as H2O & ROH as OH- & RO-

E1 or E2 ?
[1]

+ NaOH
Cl
CH3COOH Cl
Cl
-

80oC H2O

[2]

[3]

+ CH3CH2O Na

EtOH

Substitution VS Elimination

Substitution VS Elimination
Summary of SN Versus E Reactions of RX
Halide Methyl Primary Reaction SN 2 Comments SN 1 never observed SN 2 main reaction with strong NuSN 2 & E2 (Primarily SN 2) E2 only with strong, bulky bases like K tert-butoxide SN 2 & E2 SN 1 & E1 SN 2 & E2 with strong bases/ good NuSN 1 & E1 with weak Nu- in polar protic solvents SN 1 & E1 with poor Nu- /weak bases E2 with strong bases

Secondary

Tertiary

SN 1 & E1 E2

Substitution VS Elimination

END