Summary of SN2 reactions

Summary of SN1 reactions

Summary of Factors in predicting SN1 vs SN2 mechanisms:
Nucleophile:
SN1 - Weak Nucleophile- Lone Pair
SN2 -Needs a stronger nucleophile, usually negatively charged

Alkyl Halides:
SN1 - 3o > 2o (Require dissociation to carbocation before reaction)
SN2 - CH3 > 1o > 2o (Less sterically hindered favors reaction)

Stereochemistry: For Chiral Starting Material

SN1 both inversion and retention (racemic)
SN2 inversion only

Kinetics:
SN1 rate = k[RX] Unimolecular Reaction
SN2 rate = k[RX][Nu:] Bimolecular Reaction
 Tertiary Alkyl halides

 Substitutions can occur only by SN1

 Elimination can occur by either the E1 or E2.

 With weak nucleophiles and polar solvents (H2O,

ROH) the SN1 and E1 compete.

 With strong nucleophiles (OH-, RO-) elimination

by E2 is favored
 Tertiary Alkyl halides

Tertiary alkyl halide + solvent (weak nucleophile)  Substitution SN1

Tertiary alkyl halide + strong base (NaOCH2CH3)  Elimination E2

SN1 E2
 Primary Alkyl Halides

Only the SN2 and E2 mechanisms are possible

 With most nucleophiles: primary alkyl halides give
mainly substitution products (SN2)

Decreased crowding at carbon that bears the leaving

group increases substitution relative to elimination.
 Primary Alkyl Halides

Only with very bulky, strongly basic nucleophiles

like KOC(CH3)3 , potassium tert-butoxide the E2
process is favoured.
A crowded alkoxide base can favor elimination even with
a primary alkyl halide.
 Secondary Alkyl Halides

All four mechanisms SN1, SN2, E1, and E2 are possible.

The products composition is sensitive to the nuceophile
(its strength as a nucleophile and as a base)
 Strong nucleophiles that are not strong bases favor
substitution (SN2)

 Weak nucleophiles (solvent) favor substitution (SN1)

 Strong bases favor elimination (E2)

 Secondary Alkyl halides
Strongly basic nucleophiles increase elimination E2
relative to substitution

Weakly basic nucleophiles increase substitution (SN2)

relative to elimination
 Overall Summary of SN1, SN2, E1 ,E2

CH3X RCH2X R2CHX R3CX

Methyl 1o 2o 3o
Gives SN2 No SN1 Mainly SN2 No SN2
reactions Gives mainly SN2 with strong In solvolysis gives
only except with nucleophiles SN1/E1, at lower
hindered, bulky (weak bases) temperatures SN1
strong bases I‾, CN‾, RCO2‾ is favored
e.g (CH3)3CO‾ then And mainly E2 And mainly E2
gives mainly E2 with strong with strong bases
bases RO‾, OH‾ RO‾ , OH‾