E1 REACTIONS

Saytzeffs Rules Reaction Mechanism for Alkyl Halide Rearrangement Reaction (Hydride Shift) Energy Level Diagram, Reaction Kinetics Stereochemistry

E1 stands for unimolecular elimination . It is a two-step process of elimination: ionization and deprotonation. Ionization: the carbon-halogen bond breaks to give a carbocation intermediate (a.k.a loss of leaving group- bond breaking occurs, formation of carbocation). Deprotonation of the carbocation (proton transfer- formation of new bond). The reaction is said to be unimolecular and follows first order kinetics. 2 step process:

What is E1 Reactions?

* Ionization

a carbocation intermediate * Deprotonation:of the carbocation

:Carbon halogen bond breaks to give

The reaction rate is influenced only by the concentration of the alkyl halide because carbocation formation is the slowest step

(rate-determining step). Therefore, first order kinetics apply

(unimolecular). Reaction usually occurs in complete absence of base or presence of only a weak base (acidic conditions and high temperature). E1 reactions are in competition with SN1 reactions because they

share a common carbocationic intermediate.

CHARACTERISTIC OF E1 REACTIONS
1. The rate of an E1 reaction increases as the number of R groups on the carbon with the leaving group increases.

Like an SN1 reaction, more substituted alkyl halides yield more substituted (and more stable) carbocations in the rate-determining step. Increasing the stability of a carbocation, in turn, decreases Ea for the slow step, which increases the rate of the E1 reaction according to the Hammond postulate.

2. Because the base does not appear in the rate equation, weak bases favour E1 reactions.
Strong bases like OH and OR favour E2 reactions, whereas weaker bases like H2O and ROH favour E1 reactions.

3. E1 reactions are regioselective, favouring formation of the more substituted, more stable alkene.

Zaitsevs rule applies to E1 reactions also.

MECHANISM OF THE E1 REACTIONS

Reactivity of E1 Reactions
Due to the fact that E1 reactions create a carbocation intermediate, rules present in Sn1 reactions still apply.

*secondary and tertiary carbons form more stable carbocations

SAYTZEFFS RULES IN E1 REACTIONS

the major product in elimination has the more substituted double bond.

The E1 mechanism begins with : the dissociation of the leaving group from an alkyl , producing a carbocation on the alkyl group and leaving anion to initiate E1 reaction is the same way the SN1 reactions Stability: The general stability order of simple alkyl carbocations is: (most stable) 3o > 2o > 1o > methyl (least stable)

 a polar protic solvent is prefered because the polar stabilize the carbocation and protic stabilize the anions the secondary and tertiary carbocation is more prefered because there are more stable than primary carbocation difference between E1 and SN1 must depend on 2nd step, the action of the nucleophile in E1 strong nucleophile is prefered. Strong nucleophile also strong bases, nucleophile will extract the hydrogen at the carbon instead of -carbocation. E1 more reably.

Reaction Mechanism for Alkyl Halide in E1 Reactions

Secondary and tertiary alkyl halide occur in protic solvent with weakly basic nucleophile Reaction occur more easily with tertiary alkyl halide if nucleophile not a strong base. Always in competition with SN1; both occur under same reaction condition:alkyl halide is secondary and tertiary(especially), the solvent is protic to stabilize the intermediate stage and nucleophile (weak base) E1 product is most often obtained in mixture with SN1 and very weak base with moderately vigorous nucleophile, SN1 will predominate.

CHARACTERISTIC OF THE E1 MECHANISM

Reaction Mechanism for Alkyl Halide in E1 Reactions

REARRANGEMENT REACTION (HYDRIDE SHIFT)

A 1,2 hydride shift is a carbocation arrangement in which a hydrogen in a carbocation migrates to the carbon atom bearing the formal charge of +1 (carbon 2) from an adjacent carbon (carbon 1)

ENERGY LEVEL DIAGRAM, REACTION KINETICS

Step 1: Rate Determining Step The polar and weakest bond, C+-Br-, breaks heterolytically to form a carbocation Protonation of the alcoholic oxygen to make a better leaving group Very fast and reversible Lone pairs on the oxygen make it a Lewis base Cleavage of the C-O bond allows the loss of the neutral water molecule, to give a carbocation intermediate The rate determining is endothermic, Ho = +ve value

Energy diagram for an E1 reaction:

Step 2: Transition State strongly basic and nucleophilic hydroxide ion abstracts a proton from the carbocation to form water and simultaneously the C-H bond pair shifts to complete the C=C double bond of the alkene Deprotonation by a base (a water molecule) from a C atom adjacent to the carbocation center leads to the creation of the C=C Ho for Step 2 has a negative value which is exothermic because two bond formation occurs and only one is broken Ho = exothermic = -ve because the product has lower energy than the reactant
Energy diagram for an E1 reaction:

Stereochemistry

When regiochemistry are possible during E1 reaction,the product distribution follows the saytzeff rule. The double bond goes mainly toward the most highly substituted carbon. Put differently the major product is the one with more alkyl groups on the carbon of the double bond. This is so since in E1 mechanism the leaving group is gone to give a carbocation before the choice is made as to which direction the generated double bond will go.

Thus the direction is determined almost exclusively by the relative stabilities of the olefins produced via elimination. From the heat of combustion data, it is known that olefin stability increase with alkyl substitution. Thus E1 reaction occur under thermodynamic control. The more stable product is formed preferentially. The elimination which occur under thermodynamic control are said to give the saytzeff product.

For E1 elimination, therefore, Saytzeffs Rule governs the orientation whether the leaving group is neutral or positive (this is so, since leaving group is not present when the choice for the direction of double bond is made).

SUMMARY OF E1 REACTIONS
COMPARISON OF THE E1 AND E2 MECHANISMS

REFERENCES
1. 2. 3. 4. 5. 6. Janice Gorzynski Smith, Organic Chemistry, 3rd Edition McGraw Hill International http://www.chemguide.co.uk/mechanisms/elimmenu.html http://library.tedankara.k12.tr/carey/ch5-4.html http://www.chem.ucla.edu/harding/lecsups/elim30.pdf http://www2.chemistry.msu.edu/faculty/reusch/virttxtjml/alhalrx3.htm http://www.newagepublishers.com/samplechapter/000984.pdf