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CHEM 3013

ORGANIC CHEMISTRY I CHAPTER 6

LECTURE NOTES

1.

The Alkene Functional Group

Alkenes are also called olefins, or unsaturated hydrocarbons, as compared to alkanes which are referred to as saturated hydrocarbons. In alkenes, there are two or more trivalent carbons with the presence of one or more carbon-carbon double bonds. They have the general formula CnH2n. H C H H C H

Ethylene (an alkene)

E 2p N E R G 2s Y

2p 2sp2

mix 2s and two 2p orbitals

1s Elemental Carbon -bond (two 2p orbitals on carbon

1s sp2 Hybridized Carbon in Alkenes

H H

H
-bond (1s orbital on hydrogen and sp2 orbital on carbon)

-bond (two sp2 orbitals on the carbons Bonding in Alkenes

a.

Bonding in Alkenes

Hybrid orbitals of sp2 and a p orbital combine to form a -bond and a -bond, respectively. It should be noted that a double bond is actually comprised of two two-electron bonds ( and ); this is why double bonds are shorter and stronger than single bonds. The difference between a sp3 hybrid orbital and a sp2 hybrid orbital is the amount of "s" character (25% vs 33%, respectively); since the latter has 33% it makes shorter and stronger sigma bonds to the hydrogens.

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b. Cis and Trans Stereoisomerism in Alkenes The -bonding in alkenes has substantial consequences when it comes to the conformations of the alkenes. As you will recall from our discussions about rotation around bonds in ethane and butane, it is relatively easy to rotate around a sp3-sp3 sigma bond (i.e. 3-5 Kcal/mole barrier height). Rotation around double bonds requires that the -bond first be broken (about 50-60 Kcal/mole) before we can then rotate....this requires very high temperatures and is seldom observed. This lack of free rotation around a -bond leads to stereochemical consequences, there now exists the possibility of two compounds that have the same carbon connectivity, but different 3-D arrangements of the groups. These are stereoisomers of a specific type called geometric isomers . When we have an alkene which has at least two identical atoms or groups on the two doubly-bonded carbons of the alkene we use the same cis and trans formalism we used to define stereoisomers in cycloalkanes. As shown below, the cis stereoisomers has identical groups on the same side of the alkene, whereas the trans isomer has identical groups on opposite sides of the alkene.

H C H3C C H
trans-2-butene (methyls on opposite side of alkene

H CH3 H3C H CH3 H3C

H3C C C H
cis-2-butene (methyls on same side of alkene

H3C H H3C H H

p orbitals of -bond are perpendicular to plane of page; all C's in plane BUILD A MODEL!

Very hard to rotate around a double bond; have to break a -bond to do so Stereoisomers of 2-butene

2.

Nomenclature in Alkenes

Nomenclature used for alkenes is much like that used for alkanes...except that the ending changes to ...ene . Thus any compound that ends in ene is an alkene.

a.

Common Names Some alkenes and alkenyl groups have common names that can be recognized:
Common alkenes

CH2 CH2

H3C

H3C C CH CH2 H3C

H3C CH2 CH CH2 C CH2 CH CH2


styrene isoprene

ethylene

propylene

isobutylene

alkene substituent groups

H CH2
vinyl

H CH2 CH2
allyl

CH2

CH3

isoprenyl

Common Alkenes and Substituent groups

b.

IUPAC Nomenclature 1. 2. 3. 4. 5. 6. Name the longest chain including the double bond. Drop the ane suffix of the base name and add ene Number from the end nearest the double bond. Complete the name as with alkenes Specify the cis, trans or E,Z stereoisomer isomer if indicated in structure. If more than one double bond exists in the compound, it is named as a diene, triene,
1 2 3 4 5 6 7 7 6 5 4 3 2 1

NOT

trans-3-heptene Correct 1 8 7 6 5 2 3 4

trans-4-heptene Incorrect 2 1 3 4 5 6

NOT

8 7

1,4-cyclooctadiene Correct Numbering Alkenes

1,6-cyclooctadiene Incorrect

4
H2C
1 3 H2C 2 4 5 6 1

NOT

H2C 2
3 4

Octane cannot be the principal chain if it does not contain both carbons of the alkene.

2-propyl-1-hexene CORRECT

5 2-butyl-1-pentane Incorrect

Inclusion of the double bond is more important than the longest carbon chain. 1 CH2 2 3 4 CH2 2,3-diethyl-1,3-butadiene CORRECT

CH2

CH2
NO! see above

Lowest numbering of chain with maximum number of double bonds

CH
7 6 1 5 2 3 4 1 CH2 2 CH

CH2
3-allyl-6-vinyl-1,4-cycloheptadiene OR

3-(2-propenyl)-6-allyl-1,4-cycloheptadiene

CH2
3

Naming alkenes as substituent groups

c.

Naming of Stereoisomers, the E/Z Convention

As we have seen, the lack of rotation around the double bond introduces the possibilities of geometric isomerism. Geometric isomers are different compounds with different chemical and physical properties.. For example cis-1,2-dibromoethylene has a boiling point of 110 whereas the trans isomer has a boiling point of 129 C. Thus, a nomenclature method for differentiating between the different isomers is required. When we have at least two identical atoms (or groups) on the two doubly -bonded carbons, as in the compound 2-pentene (draw the structure, the alkyl groups are different...but the H's are identical), we can use the cis/trans formalism. But what about a compound

such as 1-bromo-1-chloro-1-propene? The are now four different substituents on the two carbons of the double bond; a new convention is required.

CAHN, INGOLD, PRELOG SEQUENCE RULES FOR E,Z NOMENCLATURE 1. 2. 3. 4. 5. 6. Give the groups on each carbon of a double bond, an order of priority with preference given to the groups with the heavier atom attached to the double bond. If the first atoms of two groups on a carbon are the same, then the group which has the heavier atom attached to the first atom has higher priority. If the second atoms are identical, keep moving out along the group until a difference is found. Multiple bonds count as two, three, etc., bonds to the atom attached. If the groups of highest priority are on the same side of the double bond, name the isomer Z (Zusammen). If the groups of highest priority are on the opposite side of the double bond, name the isomer E (Entgegen). high priority C
low priority

high priority C
low priority

high priority C
low priority

low priority

C high priority

Z (zusammen)....together The E/Z Nomenclature of Alkene Stereoisomers

E (entgegen)....across

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Case 1: 3-chloro-2-pentane Identical Compounds

H3C C H3C C

Cl C2H5

H3C H3C

Cl C C C2H5

Exactly the same groups; therefore E/Z meaningless Case 2: Z-1-bromo-1-chloro-1-propene

LOW

H C C

Cl Br

LOW HIGH (at# Br > Cl)

HIGH H3C (at# C > H)

Case 3: Z-3-propyl-2-heptene

SAME

LOW

H C C

CH2CH2CH2 H LOW CH2CH2CH2 CH3 HIGH


SAME

HIGH H3C

E/Z Priority Rules

H C C

X X

H C C

C X C X

C C C X C C
E/Z priority assignments of alkenes and alkynes

C C X C

d.

Relative Stabilities of Alkene Geometric Isomers

Trans isomers are more stable than cis isomers because of steric destabilization of the cis isomer. In 2-butene this destabilization favors the trans isomer by 0.69 Kcal/mole, but in 2,2,6,6tetramethyl-3-hexene (draw the structure of both isomers) the trans isomer is favored by 6.3 Kcal/mole. Additional alkyl substituents on the double bond of the alkene stabilizes the alkene...unless steric effects become too severe.

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CIS TRANS

H H H H C C C H H H C H
steric interaction
SMALL

H C

C H H H H

C H C H H

BIG steric
interaction Steric destabilization of cis-alkenes

3.

Addition of Hydrogen Halides to Alkenes( Electrophilic Addition Reactions )

Polar molecules add across double bonds in a predictable fashion. The electrons in a -bond are relatively weakly held by the carbon atoms ( -bond strength ~50-60 Kcal/mole). Thus they are available to react with a suitable electron-deficient species; alkenes are weak nucleophiles. When this occurs a new sigma bond is formed, and an electron deficient carbon (a carbocation or carbonium ion) is formed. When an alkene reacts with an electrophile ( in the case of a hydrogen halide HX...a proton), donation of -electrons from the alkene creates a new C-H bond and an intermediate carbocation (empty p orbital). This then reacts with a nucleophile ( in the case of hydrogen halides... a halide anion) to form the observed product. `
Alkene acting as a Nucleophile; a source of electron density Intermediate The empty p orbital is now an electrophile Product Net addition of both X and Y to the two ends of the alkene

C
X+ NOTE direction of curved arrows.

C X
Y-

C X

C Y

Electrophile; an electron poor species

An electron rich species (a nucleophile)

The basic mechanism of electrophillic addition to alkenes

a.

Markovnikov's Rule

Unsymmetrical alkenes often give a highly regioselective reaction (selective addition of an unsymmetrical reagent to an unsymmetrical alkene). The favored product results from the addition of the electrophile (proton, in the case of hydrogen halides) to the carbon which has the least alkyl

substitution or greatest hydrogen substitution. This is often referred to as the Markovnikov Rule after a Russian Chemist who first observed this effect in 1869. The rule is often stated as a slogan :

Them that has gets.


Them being carbons bearing the greatest number of hydrogen atoms...and gets being the proton. Markovnikov's Rule is an empirical rule (based on observations of great numbers of examples, but it is based on a simple theoretical explanation. Markovnikov's rule favors the product which passes through the most stable carbocation intermediate. H H2C H2C CH
HBr Br-

CH
2 carbocation

Br observed
product

Br H2C CH H
Brnot obtained

1 carbocation Regiochemistry of addition of HBr to an unsymmetrical alkene

b.

Carbocation Stability

Overlap between the empty p orbital of a carbonium ion center and the sp3 orbital of an adjacent alkyl group creates a stabilizing effect. This overlap results in some electron density being shared with the carbonium ion, somewhat helping the electron deficiency. This phenomenon is called Hyperconjugation and is a very important concept which will reoccur throughout the course. The more nearby alkyl groups the greater the effect. Thus the order of stability of carbocations is: Tertiary > Secondary > Primary > Methyl Thus in the case of addition of HBr to 1-hexene, the major product is 2-bromohexane (as predicted by Markovnikov's Rule) because addition of the electrophile to the double bond at the number one carbon gives the more stable secondary carbocation at the number 2 carbon.

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Relative Stability of Carbocations (Carbonium ions). Tertiary 3

>

Secondary 2

>
H H H3C

Primary 1

>
H H H

Methyl

H3C H3C

H3C CH3 H3C

filled sp3 orbitals

empty p orbital

H H
Hyperconjugation between the empty p orbital and adjacent sigma bonds formed from sp3 orbitals helps to stabilize the carbocation.

Carbocation stability is caused by hyperconjugation

c.

Carbonium Ion Rearrangements

In some cases, an initial carbonium ion intermediate will migrate to a different portion of the molecule by shifting a nearby alkyl group or hydride. This is done so as to produce a more stable carbocation. This will give, after trapping by the nucleophile, a rearranged product. The driving force for all these rearrangements is to form a more stable intermediate carbocation! (i.e. primary to secondary, secondary to tertiary, etc.)
STEP 1: Electrophillic Addition Intermediate is a follows Markovnikov secondary cation Rule CH3 CH3 H Cl H3C H3C C CH2 C CH3 C CH H3C H3C H Note direction of STEP 2: curved arrows. Rearrangement methyl group shift...... forms tertiary carbocation H3C H3C CH3 C H CH3

Cl-

H3C H3C

CH3 C CH CH3

Cl 2-Chloro-3,3-dimethylbutane 17% of product mixture

Cl-

H3C

Cl CH3 C C H CH3 CH3

2-chloro-2,3-dimethylbutane 83% of product mixture Rearrangement of Carbonium Ions

4.

Hammond Postulate

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Certain reactions have their product distributions determined by the rates of a pair of competitive pathways. Since these reactions do not involve product equilibration, it is the relative height of the transition states leading to the two products that determines the ratio of the two products. Pathways with lower barriers will occur faster, hence more of the reactant will cycle over to this product. These reactions are said to occur under kinetic control.
TS 2

TS 1 E N E R G Y

+ HBr

Br

Br

REACTION COORDINATE The transition state leading to the secondary carbonium ion (TS 1) will have some of the structure of this species. This transition state will be lower in energy than the transition state leading to the primary carbonium ion (TS 2), which has some of the structure of the less stable primary carbonium ion. Thus the rate at which 2-bromopropane will be formed is higher than that for 1-bromopropane; 2-bromopropane will be the predominate product.

Hammond's Postulate Applied to Alkene Addition

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