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STRUCTURE, NOMENCLATURE, PROPERTIES, AND REACTIONS OF UNSATURATED HYDROCARBONS

(ALKENES, ALKYNES, AND AROMATIC COMPOUNDS)

Prof. Christian Paul P. de la Cruz, Ph.D. (cand.)

STRUCTURE, NOMENCLATURE, PROPERTIES, AND REACTIONS OF UNSATURATED HYDROCARBONS (ALKENES, ALKYNES, AND AROMATIC COMPOUNDS) Prof. Christian Paul

Outline

  • 12.1 Nomenclature of alkenes

  • 12.2 Geometry of alkenes

  • 12.3 Properties of alkenes

  • 12.4 Addition polymers

  • 12.5 Alkynes

  • 12.6 Aromatic compounds and benzene

  • 12.7 Nomenclature of benzene derivatives

  • 12.8 Properties and uses of aromatic compounds

Unsaturated hydrocarbons

Contain one or more double or triple bonds between carbon atoms and belong to one of the three classes:

Unsaturated hydrocarbons • Contain one or more double or triple bonds between carbon atoms and belong

Simplest unsaturated hydrocarbons

What can you say about the bonding patterns of these unsaturated hydrocarbons?

Simplest unsaturated hydrocarbons • What can you say about the bonding patterns of these unsaturated hydrocarbons

Why considered unsaturated?

12.1 The nomenclature of alkenes (olefins)

General formula C n H 2n (same as that of cycloalkanes)

Number of structural isomers increases as the number of carbon chain increases

IUPAC rules for naming alkenes,

12.1 The nomenclature of alkenes ( olefins ) • General formula C H (same as that

Solution to learning check 12.1

In each of these alkenes, the double-bonded carbons occur at positions 1 and 2.

  • a. 3-bromo-1-propene

  • b. 2-ethyl-1-pentene

  • c. 3,4-dimethylcyclohexene

For alkenes with more than one double bonds

Important components of natural and synthetic rubber

Nomenclature is similar to alkenes with one double bond, except that the endings indicate the number of double bonds present in the molecule

E.g.,

For alkenes with more than one double bonds • Important components of natural and synthetic rubber

Solution to learning check 12.2

  • a. The chain is correctly numbered from the right to give 2-methyl-1,3-butadiene

  • b. The chain is correctly numbered from the left to give 2-methyl-1,3,6-octatriene

  • c. 7-bromo-1,3,5-cycloheptatriene

12.2 The geometry of alkenes

Hybridization involves mixing a 2s orbital and two 2p orbitals to form three hybrid sp 2 orbitals

12.2 The geometry of alkenes • Hybridization involves mixing a 2 s orbital and two 2
• sp 2 hybrid orbitals lie in the same plane and are separated by angles of

sp 2 hybrid orbitals lie in the same plane and are separated by angles of 120°

unhybridized 2p orbital of the carbon atom is located perpendicular to the plane of the sp 2 hybrid orbitals

Geometry of ethylene (ethene) – its planar!

Geometry of ethylene (ethene) – its planar!
Geometry of ethylene (ethene) – its planar!

Geometric isomerism in alkenes

Presence of a double bond prevents the free rotation of the atoms around the carbon (unlike in alkanes)

Geometric isomers – the cis- and the trans- isomers

Geometric isomerism in alkenes • Presence of a double bond prevents the free rotation of the

cis-, trans- isomers are chemically distinct

cis- , trans- isomers are chemically distinct

Conditions of cis-trans isomerism

cis-trans? YES! Why?

Conditions of cis-trans isomerism cis-trans ? YES ! Why? cis-trans ? NO ! Why?

cis-trans? NO! Why?

Conditions of cis-trans isomerism cis-trans ? YES ! Why? cis-trans ? NO ! Why?

Consider again… cis-trans? NO! Why?

Consider again… cis-trans ? NO ! Why?
Consider again… cis-trans ? NO ! Why?

Solution to learning check 12.3

a.

This

structure

does

not exhibit geometric

isomerism because there are two H’s attached to the carbon at position 1

Solution to learning check 12.3 a. This structure does not exhibit geometric isomerism because there are
  • b. Structural formulas

c.

This

structure

does

not exhibit geometric

isomerism because there are two methyl groups

attached to the left double-bonded carbon

12.3 Properties of alkenes

Physical properties – non-polars, insoluble in water, soluble in non-polar solvents, less dense than water, and more acidic than alkanes

Physical state depends on molecular mass

Alkenes with 4 or fewer carbon chain – gas (unpleasant, gasoline-like odor) Alkenes with 5-17 carbon chain – liquid Alkenes with 18 or more – solid (waxy)

Chemical properties – more reactive than alkanes

Reactions of alkenes take place at the double bonds

• Chemical properties – more reactive than alkanes • Reactions of alkenes take place at the

Addition reactions – substance is added to the double bond; two reactants that combine to form one product

Common addition reactions involving alkenes,

  • 1. Halogenation – addition of halogens

Halogenation

addition of halogens to an alkene and the resulting product contains only carbon-carbon single bond called a haloalkane or alkyl halide – an alkane derivative

Halogenation • addition of halogens to an alkene and the resulting product contains only carbon-carbon single

E.g., bromination of 1-butene

Halogenation • addition of halogens to an alkene and the resulting product contains only carbon-carbon single

Bromination of 1-hexene

Bromination of 1-hexene

*Addition of halogens is used to quantitatively determine the degree of unsaturation (e.g., vegetable oils, margarines, etc.)

*Addition of halogens is used to quantitatively determine the degree of unsaturation (e.g., vegetable oils, margarines,

Solution to learning check 12.4

Solution to learning check 12.4
Solution to learning check 12.4

Hydrogenation

Addition of hydrogen atoms (within the double bond) in the presence of a metal catalyst such as platinum, palladium, nickel

Converts the alkene into the corresponding alkane

Hydrogenation • Addition of hydrogen atoms (within the double bond) in the presence of a metal
Hydrogenation • Addition of hydrogen atoms (within the double bond) in the presence of a metal

Polyunsaturated – high degree of unsaturation; characteristics of vegetable oils such as soybeans and cottonseed oil

Hydrogenation converts oils into low-melting point solids such as margarine and shortenings

• Polyunsaturated – high degree of unsaturation; characteristics of vegetable oils such as soybeans and cottonseed

Solution to learning check 12.5

Solution to learning check 12.5

Halogenation coupled with hydrogenation

Addition of both a halogen and hydrogen (within the double bond) – acidic compounds such as HF, HCl, HBr, and HI – to form the alkyl halide

Halogenation coupled with hydrogenation • Addition of both a halogen and hydrogen (within the double bond)

Addition of H-X results in two products? How?

Addition of H-X results in two products? How? • However, only one product is formed in

However, only one product is formed in significant amounts?

Markovnikov’s rule – in the addition of H–X to an alkene, the hydrogen becomes attached to the carbon atom that is already bonded to more hydrogens, e.g.,

Addition of H-X results in two products? How? • However, only one product is formed in

Solution to learning check 12.6

  • a. The major product will be the one where H attaches to the CH carbon:

Solution to learning check 12.6 a. The major product will be the one where H attaches
  • b. Position 1 on the ring has an attached hydrogen, whereas position 2 does not have any attached hydrogens. Thus, H attaches to position 1.

Solution to learning check 12.6 a. The major product will be the one where H attaches
Solution to learning check 12.6 a. The major product will be the one where H attaches

Hydration

Water adds to carbon-carbon double bonds to give alcohols in the presence of an acid catalyst such as sulfuric acid

Water molecule is split and the –H attaches to one carbon of the double bond, and –OH attaches to the other carbon

Follows the Markovnikov’s rule

Hydration • Water adds to carbon-carbon double bonds to give alcohols in the presence of an

hydration of alkenes provides a convenient method for preparing alcohols on a large scale

• hydration of alkenes provides a convenient method for preparing alcohols on a large scale

Alkene hydration in living system

Make use of an enzyme (e.g., fumarase) instead of sulfuric acid

Alkene hydration in living system • Make use of an enzyme (e.g., fumarase) instead of sulfuric
Alkene hydration in living system • Make use of an enzyme (e.g., fumarase) instead of sulfuric

Solution to learning check 12.7

  • a. Markovnikov’s rule predicts that H will attach at position 1 to give:

Solution to learning check 12.7 a. Markovnikov’s rule predicts that H will attach at position 1
  • b. Structural formula,

Solution to learning check 12.7 a. Markovnikov’s rule predicts that H will attach at position 1

Reaction map for alkenes

Reaction map for alkenes

12.4 Addition polymers

In the presence of specific catalysts, alkenes undergo an addition reaction (polymerization) with one another to form addition polymers – very large molecule made up of repeating units (monomers)

12.4 Addition polymers • In the presence of specific catalysts, alkenes undergo an addition reaction (
12.4 Addition polymers • In the presence of specific catalysts, alkenes undergo an addition reaction (

Other polymers

Other polymers Copolymer
Other polymers Copolymer

Copolymer

53
53

Solution to learning check 12.8

The double bond becomes a single bond:

Solution to learning check 12.8 • The double bond becomes a single bond:

12.5 Alkynes

Unsaturated hydrocarbons characterized by the presence of a triple bond between carbon atoms

Rarely found in nature Physical properties – similar with alkanes and alkenes Chemical reactivity – similar with alkenes (addition reactions)

But, alkynes consume twice as many moles of addition reagents as alkenes

Acetylene (ethyne) is the simplest and most important

12.5 Alkynes • Unsaturated hydrocarbons characterized by the presence of a triple bond between carbon atoms

Geometry of alkynes

Geometry of alkynes
Geometry of alkynes
Geometry of alkynes

Alkyne nomenclature

Alkynes are named in exactly the same ways as alkenes, except the ending -yne is used:

Alkyne nomenclature • Alkynes are named in exactly the same ways as alkenes, except the ending
Alkyne nomenclature • Alkynes are named in exactly the same ways as alkenes, except the ending

Solution for learning check 12.9

Each chain is correctly numbered from the right.

  • a. 2-pentyne

  • b. 5-methyl-2-hexyne

12.6 Aromatic compounds and the benzene structure

Aromatic compounds - organic compounds containing the characteristic benzene ring or its structural relatives

12.6 Aromatic compounds and the benzene structure • Aromatic compounds - organic compounds containing the characteristic

Research: discovery of benzene

Some are known for their aromas (not all have fragrance) Aliphatic compounds – any organic compound that is not aromatic

Nature of benzene cyclic structure

Benzene is clearly unsaturated but does not show reactivity like alkenes or alkynes do

Very few reactions, very slow to react and requires heat and catalysts

Benzene must be a ring with alternating single and double bonds between carbon atoms

Nature of benzene cyclic structure • Benzene is clearly unsaturated but does not show reactivity like
Nature of benzene cyclic structure • Benzene is clearly unsaturated but does not show reactivity like

Geometry of benzene

Each carbon atom has three sp 2 hybrid orbitals and one unhybridized p orbital

A single sigma bond between carbons of the benzene ring is formed by the overlap of two sp 2 orbitals, one from each of the double-bonded carbons

The third sp 2 hybrid orbital of each carbon forms a single sigma bond with a hydrogen

The unhybridized p orbitals of each carbon overlap sideways above and below the plane of the carbon ring to form two delocalized pi lobes that run completely around the ring in the shape of a double Conclusion:

Geometry of benzene • Each carbon atom has three sp hybrid orbitals and one unhybridized p

torus

Geometry of benzene • Each carbon atom has three sp hybrid orbitals and one unhybridized p

Substituted benzene ring

Substituted benzene ring • only one hydrogen atom or group can be attached to a particular

only one hydrogen atom or group can be attached to a particular position on the benzene ring

Substituted benzene ring • only one hydrogen atom or group can be attached to a particular

12.7 Nomenclature of benzene derivatives

The following guidelines are all based on the IUPAC aromatic nomenclature system. THEY ARE NOT COMPLETE, and YOU WILL NOT BE ABLE TO NAME ALL AROMATIC COMPOUNDS BY USING THEM. However, you will be able to name and recognize those used our class.

12.7 Nomenclature of benzene derivatives • The following guidelines are all based on the IUPAC aromatic

Solution for learning check 12.10

Numbers or the term meta may be used:

  • a. 1,3-diethylbenzene or m-diethylbenzene

  • b. The compound must be named as a derivative of cyclopentane. The correct name is 1-chloro-3- phenylcyclopentane

  • c. Numbers must be used when there are three groups: the name is 1,2,3-tribromobenzene

  • d. If the compound is named as a derivative of benzoic acid,

then the methyl group is at position 2. The name is 2- methylbenzoic acid

12.8 Properties and uses of aromatic compounds

Physical properties – similar to alkanes and alkenes

Nonpolar and thus insoluble in water

Hydrophobic characteristic plays an important role in the chemistry of some amino acids and proteins

Aromatic rings are relatively stable chemically

benzene often reacts in such a way that the aromatic ring remains intact

benzene does not undergo the addition reactions

The predominant type of reaction of aromatic molecules is substitution – one of the ring hydrogens is replaced by some other group

Polycyclic aromatic compounds

A derivative of benzene in which carbon atoms are shared between two or more benzene rings

Simplest polycyclic aromatic compound,

Polycyclic aromatic compounds • A derivative of benzene in which carbon atoms are shared between two

Original active ingredient in mothballs

complex polycyclic aromatic compounds are known to be carcinogens – chemicals that cause cancer

• complex polycyclic aromatic compounds are known to be carcinogens – chemicals that cause cancer
• complex polycyclic aromatic compounds are known to be carcinogens – chemicals that cause cancer

END OF CHAPTER. THANK YOU FOR YOUR ATTENTION.

Prof. Christian Paul P. de la Cruz, Ph.D. (cand.)

END OF CHAPTER. THANK YOU FOR YOUR ATTENTION. Prof. Christian Paul P. de la Cruz, Ph.D.