REACTIONS OF ALKENES

ELECTROPHILIC ADDITION

ADDITION REACTION
An addition reaction is one in which the two reactants add together to make the product

A + B

AB

with no other pieces lost or left over.

ELECTROPHILIC ADDITION TO DOUBLE BONDS
X

C C
electrophilic reagent

+ EX

C C
E

EXAMPLES:
explained later

C C

+

conc.

Cl C C H H2SO4 OH C C
H

HCl

C C

+

H2O

C C

+

H2SO4

c onc .

0 oC

OSO3H C C H

ADDITION OF HCl

A LOOK AT THE REACTANTS

HCl C C H What is the nature of the reagent : concentrated HCl .ADDITION OF CONCENTRATED HYDROCHLORIC ACID TO AN ALKENE Cl C C + conc.

CONCENTRATED HYDROCHLORIC ACID Concentrated hydrochloric acid is HCl (g) dissolved in H2O until no more will dissolve: HCl + H2O H3O + + Cl - Since HCl (g) is a strong acid. major species present H O H + H O H H Cl no HCl - . it is almost completely ionized and dissociated in water.

ELECTROPHILE ( NEW TERM ) The hydronium ion is an electron-pair acceptor (Lewis acid) or an ……….a proton donor.. ELECTROPHILE ( = electon-loving ) B + H O H H LEWIS ACID B H + (simplified) The hydronium ion is also a Bronsted acid . .

ADDITION OF CONCENTRATED HYDROCHLORIC ACID TO AN ALKENE Cl C C + conc. HCl C C H What is the nature of the reactant : an alkene .

. electron pair donor .NUCLEOPHILE pi bond has a high electron density ( NEW TERM ) NUCLEOPHILE ( = nucleus loving ) LEWIS BASE Alkenes are electron-pair donors (Lewis bases) or a .

but a strong acid may not be a good electrophile and vice versa. .SIMILARITIES BASE = NUCLEOPHILE ACID = ELECTROPHILE All Lewis bases are nucleophiles. but a strong base may not be a good nucleophile and vice versa. All Lewis acids are electrophiles.

A reactant that forms a strong bond (stable product) is a good base.DIFFERENCES kinetic parameters nucleophile electrophile relate to the rate of reaction thermodynamic parameters base acid relate to the position of an equlibrium (bond energies) EXAMPLE A reactant that reacts fast is a good nucleophile. .

MECHANISM What is the mechanism of the reaction? .

usually by using the curved arrow formalism that we learned in drawing resonance structures. It shows all of the chemical species that are formed during the course of the reaction It also shows which bonds are broken and which are formed.MECHANISM A mechanism is a step-by-step account of what happens during a reaction. .

. .. adduct note use of arrows = movement of electron pairs . This mechanism was determined by chemists doing many investigative experiments. C C + MECHANISM slow step 1 C C + H step 2 C C H H electrophile (H3O+) intermediate ( carbocation ) Intermediates are chemical species formed during a reaction but are not products..Here is the mechanism for the electrophilic addition of HCl. : Cl : : Cl : . nucleophile .

sp3 HYBRIDIZATION CHANGES sp3 ... C C H ..sp2 sp2 sp2 slow . C + H C + H Cl fast . :Cl: . C C ... sp3 ..

PROVING THE MECHANISM Mechanisms are discovered by doing appropriate investigative experiments. .

PROVING THE MECHANISM . try reaction with Cl-.First. . They cannot react first.1 An example of some experiments that prove the mechanism follow…. sodium ion (Na+) and/or water are not able to start the reaction.. EXPERIMENT ONE H2O C C + NaCl no reaction NaCl = Na+(aq) and Cl-(aq) Conclusion : The species chloride ion (Cl-).

EXPERIMENT TWO or H3PO4 : Cl : C C H C C + NaCl H2SO4 H2O Conclusion : Acid is needed. Any acid will work. H2O).2 If you add acid to the previous reagents (NaCl.PROVING THE MECHANISM . . This suggests that H3O+ reacts in the first step. the reaction starts immediately. not Cl-.

the faster the reaction goes.PROVING THE MECHANISM .3 The more acid you add. The rate is faster at pH 1 than at pH 5 or pH 7. The reaction does not work in basic solution. EXPERIMENT THREE “acid catalysis” C C + NaCl vary pH [H+ ] H2O : Cl : C C H Conclusion : The rate of the reaction depends on the concentration of the acid : rate = K [alkene] [H+ ] Acid (H3O+) must be involved in the first step. .

EXPERIMENT FOUR NaBr NaI . they will also form products. H : I: C C H 3 products C C + HCl H2O Conclusion : H and Cl do not add at the same time in a single step.PROVING THE MECHANISM . There must be a first slow step that creates an intermediate that can react with Br. .. : Cl : C C ...4 If you add “extraneous” halide ions to the reaction mixture.as well as Cl-. H : Br: C C .and I.

5 The halide ions react only in proportion to their relative concentrations in the solution. There is no difference between the halides. : Cl : C C H .PROVING THE MECHANISM . . : Br: C C H [NaCl] [NaBr] 1M 2M 1M 1M 1M 3M Rate all are the same RCl / RBr Product Ratio 1:1 2:1 1:3 “Statistical” Result Conclusion: Halides are not involved in slow step.. EXPERIMENT FIVE rate = K[alkene][H+] C C + NaCl + NaBr H2SO4 H 2O ..

6 If the molar concentrations of HCl and HBr are the same..PROVING THE MECHANISM . EXPERIMENT SIX . rate = K[alkene][H+] . the reactions shown proceed at the same rate.. : Cl : C C + HCl H2O C C . : Br: C C H + HBr H2O C C H no rate term for X- HI (at the same molarity) also gives the same rate.

Cl.. Many additional experiments have been done to prove this mechanism. not the other way around. We will not detail them all here..if present) .adds second. : C C + (or Br. : Cl . MECHANISMS ARE PROVED BY EXPERIMENT..or I. .PROVING THE MECHANISM These experiments are consistent with the mechanism. : Cl : slow step 1 C C + H fast step 2 C C H H (H3O+) H+ Adds first . .

PHYSICAL ORGANIC CHEMISTRY Organic chemists who devise experiments to study (prove) reaction mechanisms are called PHYSICAL ORGANIC CHEMISTS If they study mechanisms by following the rates of reactions (kinetics) under various conditions they may be called KINETICISTS CHEMICAL KINETICS The study of reaction rates. .

It is convenient to classify all of these reactions under the type of mechanism that they share. The addition of HCl to an alkene is an example of a type of mechanism that is shared by a number of other reactions. In the current chapter we will study ELECTROPHILIC ADDITION REACTIONS .MECHANISTIC FAMILIES We often find that several reactions share the same basic mechanism.

C Cintermediate + HCl ( carbocation ) CCl 4 C C Br H C Br C C C E-X+ADD Br OTHER REAGENTS ANALOGOUSLY TO H-Cl 2 .OTHER ELECTROPHILIC ADDITIONS GENERALIZED MECHANISM nucleophile XC C E+ step 1 X C C E Cl slow C C + E step 2 fast electrophile conc.

WHEN PATHWAYS COMPETE .

MARKOVNIKOFF RULE REGIOSELECTIVITY .

. REGIOSPECIFIC Only one of the possible products is formed (100%).THIS IS A REGIOSELECTIVE REACTION CH3 CH3 C CH2 HCl CH3 CH3 >90% CH3 Cl C CH3 + CH3 CH CH2 Cl major <10% minor REGIOSELECTIVE Compare One of the possible products is formed in larger amounts than the other one(s).

...MARKOVNIKOFF RULE PREDICTING THE MAJOR PRODUCT When adding HX to a double bond. the anion X adds to the most highly substituted carbon ( the carbon with most alkyl groups attached).. the hydrogen of HX goes to the carbon which already has the most hydrogens CH2 + HCl CH3 Cl major product . conversely..

EMPIRICAL = DETERMINED BY OBSERVATION He had no idea why the reaction worked this way. only that as a general rule it did give the stated result. .AN “EMPIRICAL” RULE Markovnikoff formulated his rule by observing the results of hundreds of reactions that he performed.

CH 3 + HCl CH 3 Cl l CH 2 CH 3 Cl + HCl CH CH 2 + HCl CH CH 3 Cl All these reactions follow the Markovnikoff Rule. .SOME ADDITIONAL EXAMPLES Only the major product is shown .all are regioselective.

STABILITY OF CARBOCATIONS Determined “empirically” by careful observation. but also predicted by theory. .

MARKOVNIKOFF RULE ANOTHER WAY TO STATE THE RULE When the reaction forms the carbocation intermediate. the most highly substituted carbocation is favored : tertiary > seconday > primary. least favored methyl carbocation primary carbocation secondary carbocation R + CH3 CH2 + R CH R + R R most tertiary carbocation favored (lowest energy) C + R .

THE BEST CARBOCATION FORMS FASTEST CH3 slower faster primary CH3-CH-CH2 CH3 + CH3-C-CH3 tertiary low + energy CH3 CH3-C=CH2 + H3O+ major CH3 CH3-C-CH3 CH3 CH3-CH-CH2-Cl minor Cl .

. the reaction will proceed predominantly via the pathway that involves the lowest energy intermediate.Conclusion: If more than one carbocation intermediate is possible.

WHY MECHANISMS ARE IMPORTANT .

THE MARKOVNIKOFF RULE CANNOT ALWAYS PREDICT THE RESULT! CH CH CH3 EXAMPLE Both carbons of the double bond have the same number of hydrogen atoms attached! WHAT IS THE PRODUCT? You must examine the mechanism. The reaction yields the product that results from the lowest energy carbocation. .

NOT THE NUMBER OF HYDROGENS.THE STRUCTURE OF THE CARBOCATION IS THE MOST IMPORTANT FACTOR. WE NOW KNOW MORE THAN MARKOVNIKOFF DID ! .

no resonance + CH CH CH3 + CH CH CH3 (+) H (+) (+) H secondary. with resonance BETTER CH CH CH3 H Cl CH CH CH3 Cl H Major Product Minor Product .EXAMINATION OF THE CARBOCATIONS REVEALS THE ANSWER CH CH CH3 secondary.

WHAT HAPPENS IN A “SYMMETRICAL” ALKENE? (“symmetrical” = similar substitution at both carbons) each carbon would form a secondary carbocation CH3CH2-CH=CH-CH3 conc each carbon has one hydrogen 2-pentene HCl CH3CH2-CH2-CH-CH3 + each carbon has one alkyl group CH3CH2-CH-CH2-CH3 Cl 2-chloropentane 50/50 Cl 3-chloropentane .

SCOPE OF THE ADDITION OF HX .

HBr AND HI REACT THE SAME WAY (same mechanism and same regioselectivity) major +HCl conc minor CH3 Cl CH3 Br CH3 I Markovnikoff product + CH2Cl H CH2Br +HBr conc + H CH2I H + HI conc + HF REACTS ONLY UNDER SPECIAL CONDITIONS .HCl.

. :X: C C H C C + H step 2 H HCl usually adds. (polyhydrogenfluoride -pyridine-tetrahydrofuran at 0o C) .. but often requires heating HBr and HI add readily at room temperature..discussed later HF is difficult. . but will add with special solvents to give moderate yields.SCOPE OF THE REACTION C C + slow step 1 . HBr adds differently if peroxides are present . : X: .

ADDITION OF OTHER HX (H2O and H2SO4) H2O and H2SO4 can also add depending on the conditions major conc minor + H2SO4 CH3 OSO3H CH3 OH + CH2OSO3H H CH2OH H + H2O H2SO4 + This is covered on the next set of slides. .