Reacciones de Alquenos:

Introduction: Additions to Alkenes

Generally the reaction is exothermic because one are converted to two bonds

and one

bond

The electrons of the double bond are loosely held and are a source of electron density, i.e. they are nucleophilic + Alkenes react with electrophiles such as H from a hydrogen halide to form a carbocation

The carbocation produced is an electrophile

It can react with a nucleophile such as a halide

Insert top scheme pg 331

In addition reactions the alkene changes from a nucleophile in the first step to an electrophile in the second

Electron-rich atoms or molecules (nucleophiles) are attracted to electron-deficient atoms or molecules (electrophiles)

Addition Reactions
The pi ( ) bond is easily broken, which makes double and triple bonds very reactive. In the addition reaction, reactants are added to the carbon atoms in the double or triple bond.
5

Reacciones de Alquenos

Alkenes react with many electrophiles to give useful products by addition (often through special reagents) Haluros (adicion H-X) alcoholes (adicion H-OH) dihaluros (adicion X-X) alkanes (adicion H-H) halohidrinas (adicion HO-X) dioles (adicion HO-OH)
6

REACCIONES DE ADICION
Son caractersticas de los compuestos insaturados: alquenos y alquinos Nube de electrones
C C

disponibles para electrfilos

ADICION ELECTROFILICA
se rompe el enlace y el par de ese usa en la formacin de dos nuevos enlaces sp3 YZ Y Z

Reaccin de adicin a un alqueno

sp2

C C
Se combinan dos molculas para dar una sola Inversa de la eliminacin
7

Electrophilic Addition of HX to Alkenes

General reaction mechanism: electrophilic addition Attack of electrophile (such as HBr) on bond of alkene produces carbocation and bromide ion Carbocation is itself an electrophile, reacting with nucleophilic bromide ion

Writing Organic Reactions

No established convention shorthand Can be formal kinetic expression Not necessarily balanced Reactants can be before or on arrow Solvent, temperature, details, on arrow

Curved Arrows in Reaction Mechanisms

Movement of a pair of electrons

Movement of one electron

Curved Arrows Show the Flow of Electrons

electron-deficient center

electron-rich center

Rules on Using Curved Arrows

1. Arrows are drawn in the direction of the electron flow

2. Curved arrows indicate the movement of electrons

3. The head of a curved arrow always points at an atom

correct incorrect

O CH3COCH3 + HO

O CH3COCH3 + HO

CH3COCH3 OH

CH3COCH3 OH

4. The arrow starts at the electron source

REACCIONES DE ADICION ELECTROFILICA

H OH

Hidratacin

Cl

Cl

Cl

C C

Halogenuros de hidrgeno

Halgenos

Cl

OH

OH OH

Halohidrinas

Hidrogenacion

Hidroxilacin
16

17

Electrophilic Addition of HX to Alkenes

General reaction mechanism: electrophilic addition Attack of electrophile (such as HBr) on bond of alkene produces carbocation and bromide ion Carbocation is itself an electrophile, reacting with nucleophilic bromide ion
18

Hydrohalogenation

In hydrohalogenation, the atoms of a hydrogen halide add to the carbon atoms of a double bond or triple bond.
H CH3 CH CH CH3 + HCl Cl CH3 CH CH CH3 H Br
19

+ HBr

Markovnikovs Rule

When an unsymmetrical alkene undergoes hydrohalogenation, the H in HX adds to the carbon in the double bond that has the greater number of H.
H Cl CH3 CH CH2 Does not form CH3 CH CH2 + HCl Cl H C with the most H CH3 CH CH2 Product that forms
20

ADICION DE HALUROS DE HIDROGENO

CH2=CH2 + CH CH MECANISMO
H Cl
-

HX
HX

CH3CH2X CH2=CHX
HX

Reactivo: HBr (g) , HCl (g)

CH3CHX2

Paso 1 (lento)

H CH3CH CH2

CH3CH=CH2

Cl-

intermediario carbocatin
Paso 2 (rpido) ClH CH3CH CH2

CH3CHClCH3
21

REGIOSELECTIVIDAD DE LA ADICIN DE HX A ALQUENOS HCl CH3CH=CH2 CH3CHClCH3 CH3CH2CH2Cl

H Cl

Regla de Markovnikov
En la adicin de HX a alquenos no simtricos, el H+ de HX se dirige al carbono con > nmero de hidrgenos

CH3CH=CH2

CH3CH

CH2

Se va a formar el carbocatin ms estable que es el ms sustituido

ORDEN DE ESTABILIDAD DE CARBOCATIONES

CH2=CH-CH2+ CH3+
metilo

<

CH2CH3+
primario

<

(CH3)2CH+
secundario

<

(CH3)3C+
terciario

<

allico

CH2

benclico ESTABILIDAD
22

Electrophilic Addition Energy Diagram:

Two step process First transition state is high energy point

23

24

Stability of Carbocations and Markovnikovs Rule

More stable carbocation forms faster Tertiary cations and associated transition states are more stable than primary cations

25

Example of Electrophilic Addition

Addition of hydrogen bromide to 2-Methylpropene H-Br transfers proton to C=C Forms carbocation intermediate More stable cation forms Bromide adds to carbocation
26

Electrophilic Addition for Syntheses

The reaction is successful with HCl and with HI as well as HBr. Note that HI is generated from KI and phosphoric acid

27

Orientacion de la adicion electrofilica: Regla de Markovnikov

En un alqueno asimetrico, el reactivo HX puede adicionarse de dos maneras distintas, pero una es preferida sobre la otra. Si una orientacion predomina, se dice que la reaccion es regiospecifica Markovnikov observo en el siglo XIX que en la adicion de HX a un alqueno, el H se une al carbono con mas hidrogenos y el X se une al otro carbono (aquel con mayor numero de sustituyentes alquilicos) Esta es la Regla de Markovnikov
28

Example of Markovnikovs Rule

Addition of HCl to 2-methylpropene is regiospecific one product forms where two are possible If both ends have similar substitution, then the reaction is not regiospecific

29

Same example:

30

31

Practice Problem:

32

Solution:

33

Practice Problem:

34

Solution:

35

Problem : Major products?

36

Problem : Which alkene?

37

Mecanismo adicion electrofilica de alquenos

38

Transition State resembles cation

39

Carbocation Formation Is the RateLimiting Step

a more stable carbocation

40

Carbocation Stabilities

Alkyl groups decrease the concentration of positive 41 charge in the carbocation

Carbocation Structure and Stability

Carbocations are planar The positively charged carbon is surrounded by only 6 electrons in three sp2 orbitals The fourth orbital on carbon is a vacant p-orbital

42

43

Carbocation Structure and Stability

The stability of the carbocation (measured by energy needed to form it from R-X) is increased by the presence of alkyl substituents Therefore stability of carbocations:

3 > 2 > 1 > +CH3

44

45

Heterolytic bond dissociations energies:

46

Stabilizing Carbocations:

47

Electrophilic Addition Reactions Are Regioselective

48

Mechanism of Electrophilic Addition: Rearrangements of Carbocations

Carbocations undergo structural rearrangements following set patterns 1,2-H and 1,2-alkyl shifts occur Goes to give more stable carbocation Can go through less stable ions as intermediates

49

Rearrangement of Carbocation
1,2-hydride shift
a more stable carbocation

50

Rearrangement of Carbocation
1,2-methyl shift
a more stable carbocation

51

Carbocation does not always rearrange

52

Carbocation Rearrangement
Ring Expansion

a more stable carbocation

53

Carbocation rearrangements:

54

Hydride Shifts

55

Alkyl (methyl) shifts

56

TRANSPOSICIONES

CH3 CH3 C H CH CH2

CH3 CH3 C H
transposicin de hidruro

CH3
+ CH

CH3

CH3

C H

CH OH

CH3

CH3 CH3 C + CH H CH3

CH3

CH3 C OH CH H CH3

El desplazamiento 1,2 de hidruro convierte al carbocatin secundario en uno terciario que es ms estable produciendo el alcohol terciario como producto mayoritario
57

Problem : mechanism?

58

HBr
H

H-shift

Br-1
Br

59

Problem : mechanism?

60

H3C

H3C CH2

CH3 CH3

CH3

CH3 CH3

CH3 CH3

CH3 Cl

CH3

61

Problem : What will be the rearranged cations?

62

Problem : mechanism?

63

Problem : carbocation structure?

64

ADICION DE HBr ANTI-MARKOVNIKOV HBr CH3CH=CH2 perxidos MECANISMO RADICALES

O C-O O O-C

CH3CH2CH2Br

1. Formacin del radical Br ROOR 2 RO

RO + HBr

ROH + Br
O C-O

35 kcal/mol

2. Adicin de Br al alqueno CH3CH=CH2 + Br CH3CHCH2Br

CH3CHBrCH2

3. Formacin del producto CH3CHCH2Br + Br

65

H-Br

CH3CH2CH2Br

Hidratacion de alquenos: Alcoholes

In hydration, H and OH from water add to the carbon atoms of a double bond or triple bond to form alcohols (OH). The reaction is catalyzed by acid H+.
H CH3 CH CH2 + HOH H+ + HOH
+

OH H CH3 CH CH2 H OH
66

Addition of Water to Alkenes: Hydration

Hydration of an alkene is the addition of H-OH to to give an alcohol Acid catalysts are used in high temperature industrial processes: ethylene is converted to ethanol

67

Addition of HOH to Alkene

What is the electrophile? What nucleophile is present in the greatest concentration?

68

HIDRATACION
CH3CH=CH2 + H2O MECANISMO 1. CH3CH=CH2 + H+
CH3CH

H+

OH CH3CH CH3

Sigue la regla de Markovnikov produciendo el alcohol ms sustituido

2 pasos como adicin de HX Catlisis cida

H CH2

Es la inversa de la deshidratacin de alcoholes E1

OH CH3CH CH3

H CH3CH CH2

+ OH2 + H2O
CH3CH CH3

- H+

ALQUINOS HgSO4 CH3CH2C CH + H2O H2SO4

OH CH3CH2C CH2

O CH3CH2C
69

CH3

Mechanism of acid-catalyzed hydration of 2-methylpropene

Figure 6.9

Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright 2000 The McGraw-Hill Companies, Inc. All rights reserved.

70

71

72

Addition of Water to Alkenes: Hydroboration

Herbert Brown (HB) invented hydroboration (HB) Borane (BH3) is electron deficient: a Lewis acid Borane adds to an alkene to give an organoborane

73

BH3 is a Lewis Acid

Six electrons in outer shell Coordinates to oxygen electron pairs in ethers

74

Hydroboration-Oxidation Forms an Alcohol from an Alkene

Addition of H-BH2 (from BH3-THF complex) to three alkenes gives a trialkylborane Oxidation with alkaline hydrogen peroxide in water produces the alcohol derived from the alkene

75

Orientation in Hydration via Hydroboration

Regiochemistry is opposite to Markovnikov orientation (anti Markovnikov ) OH is added to carbon with most Hs H and OH add with syn stereochemistry, to the same face of the alkene (opposite of anti addition)

76

Mechanism of Hydroboration

Borane is a Lewis acid Alkene is Lewis base Transition state involves anionic development on B The components of BH3 are across C=C

77

Hydroboration: Orientation in Addition Step

78

Hydroboration, Electronic Effects Give anti-Markovnikov

More stable carbocation is also consistent with steric preferences

79

Steric Preference

80

Hydroboration - Oxygen Insertion Step

H2O2, OH- inserts OH in place of B Retains syn orientation

81

HIDRATACION ANTI-MARKOVNIKOV CH3CH=CH2 1.BH3 2. H2O2, OH(CH3CH2O)2O B2H6 gas txico 2 BH3
CH2=CH2

HIDROBORACION-OXIDACION CH3CH2CH2OH

BH2CH2CH3

CH2=CH2

BH(CH2CH3)2
CH2=CH2

CH3CH2OH

H2O2, OH-

B(CH2CH3)3

MECANISMO
CH3 CH CH2

CH3

CH H

CH2 BH2

CH3

CH H

CH2 OH

H
-

BH2
+

hidrgeno en el carbono ms sustituido

alcohol menos sustituido

82

ESTEREOQUMICA DE LA HIDROBORACIN
BH2 H

OH

BH2
CH3

CH3

CH3

El tomo de boro y el hidruro se adicionan a los dos tomos del doble enlace simultneamente H2O2/ HOADICION SYN Ambos se adicionan del mismo lado del doble enlace

OH

H
Cuando el organoborano se oxida al alcohol el grupo OHocupa la posicin del boro

CH3

83

Hidrogenacion alquenos

84

Hydrogenation
In hydrogenation, hydrogen atoms add to the carbon atoms of a double bond or triple bond. A catalyst such as Pt or Ni is used to speed up the reaction.
H H H2C CH2 + H2 Pt H2C CH2 H H HC CH + 2H2 Ni HC CH H H
85

HIDROGENACION CATALITICA
H2 / Pt

CATALIZADOR
Metal finamente dividido o adsorbido sobre un soporte insoluble e inerte como carbono o carbonato de bario
CH3

CH3CH=CH2 CH3C CCH3

CH3CH2CH3 CH3CH2CH2CH3

H2 / Pt

H2 / Pd Na2CO3
Pb(AcO)4 quinolina

H3C

Para reducir alquenos Pt Pd Ni Cu

C
H

C
H

cis

Na / NH3 (lq)

H3C

C
H

C
CH3

Catalizador envenenado es aquel que est parcialmente desactivado por tratamiento del metal (Lindlar)

trans
86

DIAGRAMA DE ENERGA PARA LA PROTONACION DEL PROPENO Efecto inductivo

E

Ea1

CH3CH2CH2+

Desplazamiento de electrones a travs de enlaces debido a la diferencia de electronegatividad entre los tomos de un enlace

Ea2

+ CH3CHCH3

R R

C+

R
120

H C+ C

CH3CH=CH2

Hiperconjugacin
progreso de la reaccin

Ea2 < Ea1

carbocatin secundario

Superposicin del orbital p vaco del sp2 con el orbital de un enlace C-H vecino Los e- del enlace estabilizan la carga positiva del carbocacin dispersndola
87

MECANISMO

R R
H R2C=CR2 H

R R C C

H H

Primero el H2 se adsorbe sobre la superficie del metal, luego se rompen los enlaces y se forman enlaces H-metal. Se adsorbe el alqueno en la superficie del metal y su orbital interactua con los orbitales vacos del metal

R R C
H

R R C
H

R R

R R C C

La molcula de alqueno se desplaza sobre la superficie hasta que colisiona con un tomo de hidrgeno unido al metal, se produce la reaccin y se regenera el catalizador
88

Mechanism of Catalytic Hydrogenation

Heterogeneous reaction between phases

89

Catalytic Hydrogenation of an Alkene

Hydrogenation
Alkene + H2 Alkane Catalyst required, usually Pt, Pd, or Ni. Finely divided metal, heterogeneous Syn addition

=>

ESTEREOQUIMICA DE LA HIDROGENACION CATALITICA ADICION SYN Los dos tomos de hidrgeno se adicionan a la misma cara del doble enlace H H2 H CH3 PtO2 CH3 CH3 CH3 cis-1,2-dimetilciclohexano
H3C H H3C CH3
H H3C CH3

H2 Pd - pineno
H H

CH3

reduccin exclusivamente en la cara inferior por bloqueo del metilo

92

Reduction of Alkenes: Hydrogenation

Requires Pt or Pd as powders on carbon and H2 Hydrogen is first adsorbed on catalyst Reaction is heterogeneous (process is not in solution)

93

Syn Addition

94

Steric effect:

95

Hydrogen Addition- Selectivity

With Pt or Pd catalysts, selective for C=C. No reaction with C=O, C=N

96

Hydrogen Addition- Selectivity

97

Problem : Major Products?

98

Solid Fats from Liquid Oils

99

Hydrogenation of Oils
When hydrogen adds to the double bonds in vegetable oils, the products are solids at room temperature.

100

Halogenation

In halogenation, halogen atoms add to the carbon atoms of a double bond or triple bond.
Br Br H2C CH2 + Br2 H2C CH2 Cl Cl HC C CH3 + 2Cl2 H C C CH3 Cl Cl

101

Testing for Double and Triple Bonds

When bromine (Br2) is added to an alkane, the red color of bromine persists. When bromine (Br2) is added to an alkene or alkyne, the red color of bromine disappears immediately.
102

Fin hidrogenacion alkenes

103

Addition of Halogens to Alkenes

Bromine and chlorine add to alkenes to give 1,2dihaldes, an industrially important process F2 is too reactive and I2 too unreactive Cl2 reacts as Cl+ Cl-; Br2 is similar

104

Addition of Br2 to Cyclopentene

Addition is exclusively trans (stereospecific)

105

Mechanism of Bromine Addition

Br+ adds to an alkene producing a cyclic cation: a bromonium ion, in which bromine shares charge with carbon

106

Mechanism of Bromine Addition

Since the Br blocks one face, one must get anti (trans) addition

107

Addition of Br2 to Cyclopentene

108

109

The Reality of Bromonium Ions

Bromonium were postulated more than 60 years ago to explain the stereochemical course of the addition (to give the transdibromide from a cyclic alkene George Olah (Nobel Prize 1994) showed that bromonium ions are stable in liquid SO2 with SbF5 and can be studied directly by nuclear magnetic resonance spectroscopy

110

Halohydrin Formation

This is formally the addition of HO-X to an alkene (with +OH as the electrophile) to give a 1,2-halo alcohol, called a halohydrin The actual reagent is the dihalogen (Br2 or Cl2 with water in an organic solvent)

111

Mechanism of Formation of a Bromohydrin

112

Mechanism of Formation of a Bromohydrin

113

Mechanism of Formation of a Bromohydrin

114

115

An Alternative to Bromine

Bromine is a difficult reagent to use for this reaction N-Bromosuccinimide (NBS) produces bromine in organic solvents and is a safer source

116

MECANISMO BrBr

+
Br

bromonio asimtrico
H CH3C Br Br CH H

CH3CH

CH2

- Br -

CH3CH

CH2

Br bromuro ataca del lado opuesto al que est el bromo

ADICION ANTI

EVIDENCIA DE ADICION ANTI Br2

H H
Br

Br H H

Br

H
H

H
Br

H
-

+
Br

trans

Br

cis Br

117

FORMACION DE HALOHIDRINAS
X2, H2O R2C=CH2

Br R2C CH2
X: Cl o Br

OH 1,2-halohidrina
MECANISMO BrBr

+
Br

H CH3C OH2

Br CH2

CH3CH

CH2

- Br -

CH3CH

CH2

H2O
H CH3C OH Br CH2

-H+

118

ADICION DE HALOGENOS
Br2
Br CH3CH Br CHCH3

Bromo y cloro se adicionan al doble o triple enlace Fluor da reacciones explosivas

Iodo se adiciona pero el producto es inestable

CH3CH

CHCH3

Br2

Br CH3C Br

Br CCH3 Br

CH3C

CCH3

ORDEN DE REACTIVIDAD DE LOS ALQUENOS

CH2=CH2 < RCH=CH2 < R2C=CH2 < R2C=CHR < R2C=CR2

REACTIVIDAD
119

OxidationofAlkenes:Hydroxylation
HydroxylationaddsOHtoeachendofC=C Oxidizingagentisosmiumtetroxide Stereochemistryofadditionissyn Productisa1,2dialcoholordiol (alsocalleda glycol)

OXIDACIONDEALQUENOS
Variosproductosdependiendodelalquenoydeloxidante OXIDACIONDELENLACE SINRUPTURADELENLACE OXIDACIONDELENLACE CONRUPTURADELENLACE OXIDACIONSINRUPTURA
KMnO4,aq 25C
H O O
H H
H
-

FORMACIONDEDIOLES
H

HO
O O
H H OH OH

Mn

Na2SO3 H2O

OsO4

H O O Os O

cis1,2ciclohexanodiol

ADICIONSYN

FormationofDiolsviaOsmiumTetroxide
Hydroxylation convertstosyndiol Osmiumtetroxide,thensodiumbisulfate Viacyclicosmatediester

Problem:WhichAlkene?

OXIDACIONCONRUPTURA

OZONOLISIS

Resultadodelaoznolisiseslarupturadeldobleenlacedelalquenopara formardoscompuestoscarbonlicos,unoacadaladodledobleenlaceoriginal

Esunareaccindedegradacinyseusaparalocalizarlaposicindeun dobleenlaceydeducirlaestructuradeunalquenodesconocido Reactivo Ozono:molculaformadaportrestomosdeoxgeno

-O

+ O

-O

O O O

+O

O-

Oznolisis

1.oxidacindelalquenoporozonoparadarunoznido 2.oxidacinoreduccindeloznido

 OzonolysisofAlkenes
Cleavageofalkeneswithozoneandworkupwith zincinaceticacidleadstolesshighlyoxidized carbonsthanproductsfromcleavagewithhot KMnO4

Unsubstitutedcarbonsareoxidizedtoformaldehyde, monosubstitutedcarbonsareoxidizedtoaldehydesand disubstitutedcarbonsareoxidizedtoketones

 Ozoneaddsacrossthedoublebondtoformthe initialozonidewhichrearrangestoahighlyunstable ozonide

Theozonidesreactwithzincandaceticacidtoeffectthe cleavage

1.Oxidacindelalqueno

O
H3C CH3
O3 CCl4

O CH3-C H

O C-CH3 CH3

H3C

O O

C
H

C
CH3

CH3 CH3

C
H O

1,2,4trioxolano OZONIDO

1,2,3trioxolano

2.Oxidacinoreduccindeloznido

H3C

O O

CH3
Zn/AcOH

C
REDUCTIVA

C
O CH3
cetona
H2O2

O CH3CH
acetaldehdo

O + CH3CCH3
acetona

aldehdo cido OXIDATIVA

/H+

O CH3COH
cidoactico

O + CH3CCH3
acetona

 OzonolysisofAlkenes
Cleavageofalkeneswithozoneandworkupwith zincinaceticacidleadstolesshighlyoxidized carbonsthanproductsfromcleavagewithhot KMnO4
Unsubstitutedcarbonsareoxidizedtoformaldehyde, monosubstitutedcarbonsareoxidizedtoaldehydesand disubstitutedcarbonsareoxidizedtoketones

 SolvedProblem
AnunknownalkenewithformulaC7H12 yieldsonly thefollowingproductonoxidationwithhotKMnO4

Answer:Sincenocarbonsaremissinginthe product,thealkenemustbepartofaringinthe originalmolecule

AdditionofRadicalstoAlkenes:Polymers
Apolymer isaverylargemoleculeconsistingofrepeatingunitsof simplermolecules(monomers),formedbypolymerization Alkenesreactwithradicalcatalyststoundergoradical polymerization Ethyleneispolymerizedtopolyethylene

FreeRadicalPolymerizationofAlkenes
Alkenescombinemanytimestogivepolymer
Reactivityinducedbyformationoffreeradicals

FreeRadicalPolymerization: Initiation
Initiation afewradicalsaregeneratedbythe homolysisoftheOObondinbenzoylperoxide Thebenzoyloxyradicaladdstoethylenetoforma carbonradical

Polymerization:Propagation
Radicalfrominitiationaddstoalkeneto generatealkenederivedradical Thisradicaladdstoanotheralkene,andsoon manytimes

Polymerization:Termination
Chainpropagationendswhentworadical chainscombine,orreactwithsomeradical scavenger Notcontrolledspecificallybutaffectedby reactivityandconcentration

OtherPolymers

UnsymmetricalMonomers
Ifthedoublebondisunsymmetrical,thereaction isviamorehighlysubstituted(morestable) radical

ChainBranchingDuringPolymerization
Duringradicalpropagationchaincandevelopforksleading tobranching Onemechanismofbranchingisshortchainbranchingin whichaninternalhydrogenisabstracted

LongChainBranching
Inlongchains,ahydrogenfromanotherchainis abstracted

CationicPolymerization
VinylmonomersreactwithBrnstedorLewis acidtoproduceareactivecarbocationthatadds toalkenesandpropagatesvialengthening carbocations

Monomers

NaturalRubber:
Madefromthesapofanumberofplants, principallyHeveabrasiliensis Cruderubber(latex)isZpolyisoprene

Alkenesobtention:EliminationReactions:
Alkenes are commonly made by elimination of HX from alkyl halide: (dehydrohalogenation); using heat and KOH and dehydration from alcohols.

Elimination by the E1 mechanism

Figure 5.12

Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright 2000 The McGraw-Hill Companies, Inc. All rights reserved.

 ZaitsevsRule:FormationoftheMostSubstitutedAlkeneisFavoredwith aSmallBase Somehydrogenhalidescaneliminatetogivetwodifferentalkene products

ZaitzevsRule:whentwodifferentalkeneproductsarepossibleinan elimination,themosthighlysubstituted(moststable)alkenewillbe themajorproduct Thisistrueonlyifasmallbasesuchasethoxideisused

 Heatsofhydrogenationofthreebuteneisomers:

OverallRelativeStabilitiesofAlkenes Thegreaterthenumberofattachedalkylgroups(i.e.themore highlysubstitutedthecarbonatomsofthedoublebond),the greaterthealkenesstability

 SynthesisofAlkenesviaElimination Reactions
Dehydrohalogenation
ReactionsbyanE2mechanismaremostuseful
E1reactionscanbeproblematic

E2reactionarefavoredby:
Secondaryortertiaryalkylhalides Alkoxidebasessuchassodiumethoxideorpotassium tertbutoxide

Bulkybasessuchaspotassiumtertbutoxideshould beusedforE2reactionsofprimaryalkylhalides

 FormationoftheLeastSubstitutedAlkene UsingaBulkyBase
Bulkybasessuchaspotassiumtertbutoxidehave difficultyremovingstericallyhinderedhydrogens andgenerallyonlyreactwithmoreaccessible hydrogens(e.g.primaryhydrogens)

 AcidCatalyzedDehydrationofAlcohols
Recallthateliminationisfavoredoversubstitutionathigher temperatures Typicalacidsusedindehydrationaresulfuricacidandphosphoricacid Thetemperatureandconcentrationofacidrequiredtodehydrate dependsonthestructureofthealcohol Primaryalcoholsaremostdifficulttodehydrate,tertiaryarethe easiest

Rearrangementsofthecarbonskeletoncanoccur

 MechanismforDehydrationofSecondaryandTertiaryAlcohols:An E1Reaction Onlyacatalyticamountofacidisrequiredsinceitisregenerated inthefinalstepofthereaction

Mechanism of acid-catalyzed dehydration of tert-butyl alcohol

Figure 5.6

Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright 2000 The McGraw-Hill Companies, Inc. All rights reserved.

 CarbocationStabilityandtheTransitionState Recallthestabilityofcarbocationsis:

ThesecondstepoftheE1mechanisminwhichthecarbocationformsis ratedetermining Thetransitionstateforthisreactionhascarbocationcharacter Tertiaryalcoholsreactthefastestbecausetheyhavethemoststabletertiary carbocationliketransitionstateinthesecondstep

 TherelativeheightsofG forthesecondstepofE1 dehydrationindicatethatprimaryalcoholshavea prohibitivelylargeenergybarrier

 CarbocationStabilityandtheOccurrenceof MolecularRearrangements
RearrangementsDuringDehydrationofSecondaryAlcohols Rearrangementsofcarbocationsoccurifamorestablecarbocation canbeobtained Example

ThefirsttwostepsaretosameasforanyE1dehydration

Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright 2000 The McGraw-Hill Companies, Inc. All rights reserved.

Prob.:Howmanyalkeneproducts fromdehydration?

Solution: