CHEM 109A Elimination Reactions - KEY

CLAS

1. Predict the products of the following reactions (a-c E2, d-f E1 KEY focuses only on elimination products, in most cases there will also be substitution products.)
Br
O

a.
Br

-O

LG must be axial
O

HO
-O

Br-

are the same

-O

b.
H
H

Br

HO
-O

Br

major P (E > Z and more substituted over less substituted alkene)

Br-

-O

c.
H

Cl

-O

HO

Cl

LG must be axial
H O

major P (more substituted alkene)

Cl-

d.
I

H
H

IH 3O+
major P

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CHEM 109A Elimination Reactions - KEY

Br

CLAS

H O

e.
Br

Me shift

2o carbocation

3o carbocation

H 3O + Br-

major P
HO

f.

Br

Br

Hydride shift
O

H 2O +CH 3 Br-

major P

2. Which reactant in each of the following pairs will undergo an elimination reaction more rapidly? Explain your choice and show the mechanism.
OH Cl

OHBr

a. or E2 conditions and Br better LG so more rapid reaction.

H 2O

H 2O

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CHEM 109A Elimination Reactions - KEY

CH3O CH 3OH
Br b. or E2 conditions and LG must be axial for E2 reaction.
Br

CLAS

CH3O CH 3OH

3. For each of the following, give the major elimination product; if the product can exist as stereoisomers, indicate which stereoisomer is obtained in greater yield. a. (R)-2-bromohexane + high concentration HO-
H
H

-OH
Br

H 2O

Br-

trans is major P (cis and monosub alkene are minor)

E2

b. (R)-2-bromohexane + H2O
H

Br
H

O H H

H 3O + BrH

trans is major P (cis and monosub alkene are minor)

E1

c. trans-1-chloro-2-methylcyclohexane + high concentration CH3O-

Cl H

-OCH 3

Will remove H on C6 b/c it is axial

E2

d. trans-1-chloro-2-methylcyclohexane + methanol

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CHEM 109A Elimination Reactions - KEY

H
O
Cl

CLAS

Hydride shift H2O +CH3 Cl -

E1

e. (R)-2-bromohexane + high concentration sodium tert-butoxide

Na+
Br H H H H H H -O H O H H H H

(R)-2-bromohexane

Na+

Br-

E2 f. (2-Bromo-3-methyl-butyl)-benzene/2-bromo-3-methyl-1-phenylbutane + high concentration methoxide

Br H -O CH3

H H H

(2-Bromo-3-methyl-butyl)-benzene

BrH

CH 3

major P (dbl bond is less substituted, conjugated with benzene ring)

E2

Additional Information: Definitions Elimination rxn: in general, removal of H-X molecule and formation of double bond (alkene). A.K.A. -elimination, 1,2-elimination Zaitsevs (Saitseffs) Rule: The more substituted alkene is obtained when a proton is removed from the -C w/fewest Hs. EXCEPTIONS: If R has double bond or benzene ring, the conjugated alkene (NOT more sub) will be more stable/major P. If bulky B is used, alkene w/ bulky groups opposite each other (NOT more sub) will be the more stable/major P.

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CHEM 109A Elimination Reactions - KEY

CLAS

E2
Mech: Bimolecular, 1 step/concerted reaction: B removes proton from -C, e- go to form double bond and -C X bond breaks heterolytically so LG leaves as X-.

Br

H 2O

Br-

H
H

-OH

Rel Reactivity: Based on LG: RI > RBr > RCl > RF Based on R: 3o > 2o > 1o Regioselectivity: Usu. follows Zaitsevs rule
Br

-OH

major P, more substituted alkene

unless opportunity for formation of conjugated double bonds

I

major P, conjugated diene

minor P, more substituted, but isolated diene

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CHEM 109A Elimination Reactions - KEY

Cl

CLAS

major P, dbl bond conjugated w/ benzene ring

minor P, more substituted, but dbl bond isolated from benzene ring

OR steric hinderence for B reacting w/ H on -C (i.e. bulky base)

major P, b/c less steric hinderence

Br

-O

Tbl 9.1 If alkyl halide (R) is NOT sterically hindered and Base is Little/Moderately hindered Very hindered More sub P Less sub P W/ alkyl fluoride major P is the less substituted alkene b/c F is such a poor LG that a neg charge develops on the -C in the T.S. ~ carbanion (1o > 2o > 3o, carbanion stability b/c destabilized by e- donating alkyl groups). Stereoselectivity: Since elimination of H and X occurs in 1 step, the H-C and X-C bonds have to be in the same plane (a.k.a. periplanar) Syn-elimination (from eclipsed conformer) front attack Anti-elimination (from staggered conformer) back attack, favored b/c it is the more stable conformer & allows for back-side attack so base doesnt feel the LG as much get more E than Z.

E1
Mech: 2-step rxn 1) LG leaves to form carbocation (r.d.s.) 2) B removes H from -C (delocalization of e- b/c of hyperconjugation dec B.D.E. of H attached to sp3 C).
H 3O+
Br

Br-

*WATCH for 1,2-hydride shifts, 1,2-methyl shifts (carbocation rearrangements) to form more stable carbocation before deprotonation.

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CHEM 109A Elimination Reactions - KEY

CLAS

Rel Reactivity: Based on LG: RI > RBr > RCl > RF Based on R = rel stability of carbocations: 3o benzylic ~ 3o allylic > 2o benzylic ~ 2o allylic ~ 3o > 1o benzylic ~ 1o allylic ~ 2o > 1o > vinyl Regioselectivity: Same as E2 Stereoselectivity: W/ carbocation intermediate, both anti and syn elim possible major P has bulkiest substituents opposite each other rel to the double bond. Cyclohexanes E2 H and X must be axial (more stable conformer will NOT go E2) E1 carbocation intermediate w/ possibility of rearrangement, usually follows Zaitsevs Rule. Substitution and Elimination Compete So look at rxn conditions Tbl 9.4, 9.5and 9.6 Rxn Conditions Alkyl Halide 1o 2o 3o Rel Reactivity Stereochemistry SN1 vs. E1 SN2 vs. Poor Nuc/wk B N/A Favored Both Both Both N/A o o o o o o o 3 > 2 > 1 1 > 2o > 3o 3 >2 >1 Both E & Z (more w/ Inverted bulky Both R & S only groups opposite) E2 Strong Nuc/strong B W/ sterically hindered R or Nuc/B W/stronger B, bulkier B, higher T Only o 3 > 2o > 1o Both E & Z (more w/ bulky groups opposite, unless -C bound to 1 H and then only single stereoisomer formed)

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