Flow Charting Leaving Group Reactions

James P. Hagen
University of Nebraska at Omaha, Omaha, NE 68182

A popular trend in current organic chemisrry texts is early
introducrion toalkvl halide chemistw (e.a., Streitwieser and
~eathcock-chapter 9, ~ a d e - ~ h a ~ t 5, e iMorrison and
Boyd-Chapter 5, VollhardtChapters 6 and 7). Thus the
substitutionand elmination reactions of the halides in many
texts precede the chemistry of alkenes, which tmditi~~nnlly
was used to introduce the student to solution reactions.
While this trend has many pedagogical advantages, there is
at least one drawback: the reactions of the halides are more
complex mechanistically than ionic ar'ditions of alkenes.
The student must learn to ~ r e d i c whexher
t substitution or
elimination wi 1 occur in k a l k y l halide reaction. This is a
bewildering concept since so many factors (halide structure,
solvent, nucleophilicity and basicity of the Lewis hases
present) influence expected outcome.
As a study aid for the students, I summarize the reactions
of the halides in the form of a flow chart. This is presented as
a hierarchical series of questions in which strong hases are
ves
first located, then solvent and nucleophilicity effects are
considered, and finally attention is directed to the structure
of the halide. In this final stage stereochemical effects are
considered also.
The flow chart is equally applicable to reactions that may
involve other leaving groups such as tosylates or henzoates.
The flow chart I currently use is shown in the figure. I also
include on this handout additional information that allows
very reactive substrates (allylic and benzylic) as well as un-
reactive substrates to be considered when these structural
types are covered later in the text. I find that the flow chart
provides a good capsule review for the students both a t the
beginning of the second semester of the year course and
before the final exam.
Presented March 28, 1987, at the University of Nebraska-Lincoln,
symposium on organic chemistby teaching.
1 1 0 SN2 some E2 possible
SN2 and E2
E2

(SN2 - bimolecular. second order, inversion)

E2 C.g. of poor nucleophlles: KOHlEtOH or
E2 lithium dllsopropylamide)
Strong bare? 3O E2

SN2, no E2
SN2, little E2
slow E2; S N and
~ El possible If ionizing solvent
(SNl - unlmolecular, first order, racemizalion)
no I Good nucieophile?

\
r strongly polarizable
species e.g. RS-.
R3P. I-, Br- In a
polar solvent (weakly lo no reaction
polarizable species 2' Slow SNl, slow El
like CI- are p o d nuclsophil~s 3' SNl, E l
in polar aprotlc solvents. )

Ino no reaction
'Polar aprotic Solvents contain no OH br NH groups; e.g., acetone, dimethyllonnamide, dimethyisultoxide,
hexamethylphosphoramide. and acetonitrile. Ionizing solvents are hydroxylic; e.g., methanol, ethanol, acetic acid, and
water.
Ailylic and benzylic halides are very reactive substrates and will react it either a l o or a 3' substrate reacts.
Vinyl and phenyl substrates are quite unreactive. Very strong bases will give elimination (E2) however.

820 Journal of Chemical Education