Chs.

7 & 8: Alkenes

Alkenes (olefins): hydrocarbons containing C=C. Unsaturated less than 4 single (sigma) bonds to C. Simplest alkene = ethene C-C bond length = 1.34 average bond angle = ~120o .

H
C=C

H H

ethene (ethylene)

Orbital picture shows

&

bonding bond and above and below plane

electron density is along axis of of molecule in bond.

pi bond - sideways overlap of p orbitals

H H

H H ethene (ethylene) sigma bond - electron density along bond axis

I. Nomenclature : IUPAC rules

Alkenes 1. Select the longest carbon chain containing the double bond as the parent. Name as ethene, propene, butene, pentene, etc. (Alkane name minus ane plus ene) 2. # the C chain of parent so that C=C has the lowest possible number (locant). 5 4 3 2 1 Ex: CH3CH2CH=CHCH3 If more than one way of numbering gives lowest # to C=C, choose the way that gives the lowest #s to branch points.

6 H3C

5 4

1 2 CH 3 CH3

NOT

1 H3C

2 3

6 5 CH 3 CH3

3. Write full name #ing substitutents & listing them alphabetically.

H3C

CH3

H3C

CH3 CH3

2-pentene

2-methyl-3-hexene

4. If two or more double bonds are present, choose as the parent the longest C chain containing both and use the prefixes di, tri, tetra, etc. before ene.

H H H CH3 H H3C

H H CH2 H

1,3-pentadiene

2-ethyl-1,3-butadiene

Cycloalkenes 1. Give double bond lowest locant 1. 2. Number substituents thru the double bond so that they have the lowest possible locants. 3. List the substituents alphabetically.
4-methylcyclohexne

1-ethyl-4-methyl-1,3-cyclohexadiene

5,5-dimethyl-1,3-cyclohexadiene

Common names CH2=CH2 CH3-CH=CH2 H2C=CHH2C=CH-CH2ethylene propylene vinyl allyl (IUPAC: ethenyl) (IUPAC: 2-propenyl)

II. Cis/trans stereoisomerism Occurs in alkenes because there is no rotation about C=C

H H

CH3 CH3

H3C is not the same as H

H CH3

Geometric isomers (cis/trans) exist for every alkene which has nonidentical groups attached to both C atoms of double bond
H3C CH3CH2 CH3 -no cis/trans isomerism H

H3C CH3CH2

H cis-2 pentene H

H CH3CH2

CH3 trans 2-pentene H

cis: substituents on same side of double bond trans: substituents on opposite sides of double bond

As molecules get larger and more complex, cis/trans nomenclature gets complicated.
For cpds like: H3C CH3 use Z,E nomenclature 1. Assign priority to groups on each C of double bond 2. If high priority groups on both C's are on same side of the double bond, use Z (Zusammen - together). 3. If high priority groups on both C's are on opposite side of the double bond, use E (Entgenen -apart). high C low Z C low low high high C E C high low H CH3 CH2CH3

Assignment of priority: Cahn-Ingold-Prelog Sequence Rules 1. Assign priorities of the atoms directly attached to C atoms of the double bond according to atomic #.
higher atomic # = higher priority C(6) > H(1) N(7) > C(6) O(8) > N(7) D(2) > H(1) Isotopes = special case since they have the same atomic # Use atomic wt. # instead.

2.

If priority cannot be established by rule #1, make a similar comparison of the next atoms in each group.

3. Multiply-bonded atoms are equivalent to the same # of singly bonded atoms H

H H = -C C C H C C H

Ex:

H C

CH3 H

C -C C-H = -C C N -C N: = -C N

C C C C N C H

O = CH3

O -C O

H C H H

O = H

C H

O -C O H H

Designate the following molecules as E or Z

Br Cl H H3C H Z E O OH H3C CH2OH H CH3 Br H

III. Stability of alkenes a) cis vs trans Generally, cis isomers are less stable than trans isomers
H H3C H trans 2-butene CH3 CH3 H3C H H

cis 2-butene -less stable: higher E due to steric strain. The larger the groups on the double bond, the greater the E difference between cis and trans.

E = 2-3 kJ/mol

Energy difference is reflected in 1) interconversion equilibria and 2) heats of hydrogenation Interconversion equilibria: H
H3C H at 298K: 76% CH3

acid cat.

CH3 H3C H 24% H

G = -RTlnK = -(8.314J/K)(298K)ln(.24/.76) 2.8kJ

heats of hydrogenation:
H2, cat H2, cat

trans 2-butane

butane

cis 2-butene

Hhyd (cis)= -120 kJ/mol Hhyd (trans) = -116 kJ/mol Energy difference = 4 kJ/mol (close to 2.8 kJ, 4kJ is from while 2.8 kJ = G data) b) stability of mono - vs polysubstituted alkenes General trend:
R2C=CR2 > R2C=CHR > RCH=RCH R2C=CH2 > RCH=CH2 more stable lower Hhyd less stable higher Hhyd
H data

Explanation of observed stability trend:

-hyperconjugation occurs when a pi orbital can overlap (partially) with a neighboring sp3 orbital. only happens when C=C is substituted. In the figure, the pi orbital can interact with 3 sp3 orbitals.

-greater bond strength for sp2-sp3 bonds than for sp3-sp3 bonds. Compare CH3-CH=CH-CH3 (disub.) and CH3-CH2-CH=CH2 (monosub.) 2 sp3-sp2 bonds vs 1 sp3-sp3 and 1 sp3-sp2

Reactions of Alkenes 4 types well examine 1. electrophilic addition 2. hydrogenation (reduction) 3. oxidation 4. radical addition

Electrophilic Addition
+ nucleophile Y-Z electrophile

I. Addition of acid: H-B

-acid catalyzed

B H R2C=CHR + H-B R R H R

H-B = HX (X=Cl, Br, I) H-HSO4 H-OH

A) Mechanism

1. R2C=CHR

H B

+
R R

H R H + B

Rate determining step

2.

+
R R

H R H + B

B H R R H R

For H-Br + (CH3)2C=CH2

Outline the mechanism:

Rate law from RDS: rate = k[alkene][H-B] first order in alkene first order in H-B second order overall

B) intermediate of rxn = carbocation structure of R3C+:

R + R R -sp2 hybridized -empty p orbital -6 valence electrons

120o

Relative stabilities of carbocations effect of alkyl groups R3C+ > R2CH+ > RCH2+ > CH3+ most stable least stable 3o > 2o > 1o > CH3+

How do alkyl groups stabilize the positive charge? 1. Hyperconjugation

Overlap between vacant p orbital and an adjacent C-H bond (sp3 orbital)
H H + + H H

=
H

Not possible in methyl cation The more R groups, the more hyperconjugative interactions are possible.

2. Inductive effects
alkyl groups donate e- density by induction toward (+) charge. the more alkyl groups, the greater the stabilizing effect.

C) Orientation of addition There are two possible products from the addition of H-B
B H R2C=CHR OR H B R2C=CHR + H-B R R H R + H-B R R H R observed product

Rxn is regioselective: only one of two possible directions of addition is observed.

Markovnikovs Rule: For electrophilic addition of HB to an alkene, the acid H will become attached to the double bond C already bonded to the greater # of Hs. Predict the products:

H-Br ether

H-Cl ether

To understand:
CH3 H3C H CH3 H-Br H3C H3C Br H H CH3 or H3C H Br H CH3 CH3

Q: What does it mean to obtain only one of two possible products? A: Favored product is formed faster. RDS for two possibilities:
CH3 H3C H CH3 H-Br H3C + H H CH3 + Br-

product

H3C H

CH3 H3C H CH3

H-Br

H3C H3C

H CH3

Br-

 Shown is the energy profile for the RDS The rate is determined by the activation energy energy difference between reactant and transition state of RDS. The rate is proportional to e (-Ea/RT). The greater the Ea, the slower the reaction.

Since the Markovnikov product is the favored product, it must be formed faster, that is, with a lower Ea. Therefore its TS must be lower in energy than the TS of the nonMarkovnikov product. Could this have been predicted? Hammond Postulate: For an endothermic reaction step, the TS resembles the product. For an exothermic reaction step, the TS resembles the reactant.

For the RDS in the addn of H-B, the TS resembles the carbocation product of that step, so the more stable the carbocation, the more stable the TS, the lower the Ea, the faster the reaction. So, compare the carbocations arising from the Markovnikov and non-Markovnikov pathways.

Markovnikov pathway

H3C

H H CH3 + H CH3

3o carbocation

H3C H H3C H3C

Non-Markovnikov pathway

2o carbocation

stability of carbocations: 3o > 2o > 1o E of the Mark. TS < E of non-Mark. TS Ea (Mark. pathway) < Ea (non-Mark. pathway) So Mark. pathway is faster than non-Mark pathway

Predict the products:

H-Cl ether H2SO4 H2O

H2O, H+

All three reactions pass through the same intermediate carbocation. What is its structure?

Write the mechanism for the acid catalyzed reaction between 1-methylcyclohexene and water (the 3rd reaction)

D. Rearrangement of carbocations In some cases, more than one product may be obtained as a result of rearrangement of the carbocation intermediate.
CH3 H H3C H H + H Cl (CH3)2CH H CH3 predicted Mark. product

Example:

H-Cl ether

CH3 H3C Cl CH2CH3

rearranged product major product

Provide a mechanism for the formation of the second product.

First ask: What intermediate carbocation produced the rearranged product? A. H3C CH3 + CH2CH3

Second Q: What carbocation is originally produced (product of Mark. addition of H+)? A. H3C H H CH3 H CH3 H3C C CHCH3 H +

H-Cl

H Third Q: How do you get from initial R+ to the rearranged R+? A. H3C H CH3 CHCH3 + H3C 1,2 hydride shift CH3 + CH2CH3

Justification: conversion of a 2o carbocation to a 3o carbocation with increase in stability CH3 H3C H 2o CHCH3 + H3C CH3 + 3o CH2CH3

Other possible rearrangement: 1,2-alkyl shift

H-Cl Example:

H-Cl

Cl-

II. Addition of X2 (X2 = Cl2, Br2; F2 is too reactive; I2 is slow & not as useful) X X X
2

R2C=CR2
A. Mechanism
R R R + R Br Br

R R R

(a vicinal dihalide)

R R

Br +

R R

Br

cyclic bromonium ion

R R

Br +

R R

Br

Br R R

R R Br

B. Stereochemistry of addition = anti due to cyclic intermediate: Br- must add to side opposite to first Br.
R R Br + R R + Br Br R R R R Br

OR

R R

Br +

R R

Br + Br R R R Br R

Predict the product and give a mechanism:

Br2 CCl4

C. The Nu: in the 2nd step of the rxn can be any nucleophile.
Br + R2C CR2 Cl (NaCl) Cl I(NaI) NO3(NaNO3) Br H2O OH Br Br Br Br Br

R2C=CR2

Br

NO3

halohydrin formation

Halohydrin

C X

C OH

H2C=CH2

Br2, H2O

HO-CH2CH2-Br HO-CH2CH2-Cl

2-bromoethanol - a bromohydrin 2-chloroethanol - a chlorohydrin

Cl2, H2O

For asymmetrical alkenes, 2 products are possible.

Br2, H2O R2C=CHR R

Br OH H or R R R

OH Br H R R observed product

-halogen becomes attached to the double bond C already bonded to the greater # of H atoms

To understand:
Br R R
Br

H R

resembles 2o carbocation resembles 3o carbocation has more (+) character = point of attack by nucleophile

When nucleoophile (H2O) attacks in 2nd step, it attacks the more highly substituted C atom.
R H Br + R R .. : OH 2 Br R H R R +O: H H

- H+

Br R H

R R : O: H

Mechanism for halohydrin formation: note regiochemistry and stereochemistry

Br2 OH2 H OH CH3 Br

1.

Br

Br H OH2 + Br CH3 +O H H

Br

2. H + Br CH3 H Br +O H H CH3

3. H Br

Br

H OH + CH3 Br

HBr

CH3

III. Addition of H2O hydration 2 methods A. oxymercuration - demercuration

1.

Hg(OAc)2, H 2O

R 2C=CHR
2.

-regiochemistry = Markovnikov

- non-stereospecific

1. Hg(OAc)2, H2O

H3C

Example:

2. NaBH4

CH3CH2

CH3 OH

AcO-Hg-OAc

H H

-OAc

HgOAc H
H H

H H H

O+ OH2

-OAc O

H H H

HgOAc

HgOAc

HgOAc

H O H H

NaBH4 (exact mechanism not known)

not stereospecific - syn & anti addition is observed

B.

Hydroboration oxidation non-Mark. Addition - syn stereochemistry

BH3, THF

H2O2 , OH-

H3C
1.

CH3 CH2CH3

BH3

H2B H3C D
-----

H CH3 CH2CH3

-BH2 and -H add to the same side of the dbl bond - syn stereochemistry -BH2 is added to the less substituted C atom and -H is added to the more highly substituted C atom because that reduces crowding in the transition state. Since -BH2 is later replaced by -OH, non-Markonikov regiochemistry results.

H2B
2.

H CH3 CH2CH3

HO
H2O2, OH-

H CH3 CH2CH3

H3C D

H3C D

HC2HC

B 2H

HC2HC

H HO

HC2HC

-HO

,2O2H

-----

B2H

FHT ,3HB

2HB-H

HC2HC

HC2HC

:msinahceM

.1

CH2CH3

nys - dnob lbd eht fo edis emas eht ot dedda era 2HB dna H -( yrtsimehcoerets cirets ssel ni stluser - mota C detutitsbus ssel eht ot dedda si 2HB )yrtsimehcoiger .kraM-non - etats noitisnart ni gnidworc

H3C

CH3

BH3, THF

H2O2, OH-

HC HC H

OH

D
-HO

,2O2H

B2H

.2

H3C D

OH H CH3 CH2CH3

H2B H3C D

H CH3 CH2CH3

IV. Addition of carbene - R2C:

CR2 + R2C:

carbene is generated "in situ"

cyclopropyl ring

Example: CHCl3 KOH or KOt-bu :CCl2 (dichlorocarbene)

CH2I2

Zn(Cu)

I-CH2-Zn-I

(carbenoid - adds :CH2) - Simmons-Smith reaction

Reaction of carbenes with alkenes is stereospecific:

Cl H3C H CH3 H CHCl3 KOH CH3 CH2I2, Zn(Cu) H H Cl CH3 H H

cis

cis
CH3 CH3

cis

Cl H3C H H CH3 CH2I2, Zn(Cu) trans H CH3 CHCl3 KOH CH3 H Cl CH3 H H

trans

CH3

trans

Hydrogenation (reduction)
catalyst = Pt, PtO2, Pd/C, Ni H R R Addition is syn H R R

R2C=CR2

H2

H2, cat.

Under the relatively mild rxn conditions (Rm temp.) which reduce C=C, other multiple bonds are not reduced.
H2 phenyl groups: Pd/C

H2 carbonyl groups: PtO2

H2 PtO2

H2 cyano groups: Pd/C

Oxidation
A. Epoxidation
1. via halohydrin
via halohydrin CH3 Br2 H2O H Br OH CH3 O CH3 epoxide (oxirane)

mechanism of epoxide formation: H H Br

: O:

OH-

H Br

.. :O:CH3

: O:

epoxide (oxirane) CH3

CH3

2. via peroxyacid
O OH R O

CH3

epoxide (oxirane)
CH3

B. Hydroxylation glycol formation (glycol = cpd with vicinal hydroxy groups)

To get cis glycol:

1. OsO4, pyridine 2. NaHSO3 (aq)
H H

cis
OH OH

To get trans glycol:

RCOOOH
H

HO O H

H3O+
H OH

trans

C.

Oxidative Cleavage - 3 types 1. ozonolysis 2. permanganate oxidation 3. periodate oxidation of glycols

1. ozonolysis of alkenes

R1 R2

R3 R4

1. O3 2. Zn,H+

R1 O R2 + O

R3 R4

R = alkyl, H

2. permanganate oxidation of alkenes R H R1 R2 H H R3 H KMnO4, H+ or KMnO4, neutral R O + OH O O R2 + R3 OH CO2

KMnO4, H+ or KMnO4, neutral

R1

R = alkyl

=CH2 =CHR =CR2

CO2, carbon dioxide RCOOH, carboxylic acid R2C=O, ketone

3. periodate oxidation of glycols (result like ozonolysis) 1. OsO4, pyr 2. NaHSO3 (aq)

R1 R2

R3 R4

HO R1 R2

OH R3 R4

alkene
HIO4 R1 O R2 O

glycol

R3 R4

Radical Polymerization use fish hook arrows in mechanism

H H RO-OR nH2C=CH2 RO H H
n

3 steps in any radical reaction: 1) initiation: generation of a free radical RO OR 2RO.

2) propagation: attack of alkene by a free radical generates another free radical

RO.

H2C=CH2

RO-CH2-CH2.

RO-CH2-CH2.

H2C=CH2

RO-CH2-CH2-CH2-CH2. - generates another free radical

3) termination: ends the polymer and doesn't produce a radical

Ex: Combination of 2 radicals

R-R

Polymerization of unsymmetrical alkenes to predict product, need to take into account the stability of radicals.
n H2C=CHR RO-OR RO CH2-CHR * or RO CHR-CH2 ??

Mechanism for formation of first product:

Mechanism for formation of second product:

1. RO - OR

2RO. . RO-CH2-CHR . RO CH2-CH-CH2-CHR

R

1. RO - OR

2RO. .

2.

RO.

H2C=CHR

2.

RO.

+ .

H2C=CHR

RO-CHR-CH2
R R

. 3. RO-CH2-CHR

H2C=CHR

3. RO-CHR-CH2

H2C=CHR

. RO CH-CH2-CH-CH2

observed product

not observed

Q:
Why do radicals in step 2 & step 3 always add to the less hindered C atom? A:

So the more highly substituted radical is formed

H R RO. + H2C=CHR or RO H H R H RO H H Order of radical stability: 3o > 2o > 1o >.CH3 so the more stable radical is formed. . 1o radical . 2o radical