Reactions of Alkenes and Alkynes

Alkenes
Addition to carbon-carbon double bond  MECHANISM  Double bond is broken and in its place single bonds form to two new atoms or groups of atoms.


Addition Reactions
Hydrohalogenation  Hydration  Bromination  Hydrogenation (reduction)


Addition Reaction

Reason for reactivity of C=C

One double bond and one single bond (HH bond of H2) are replaced by three single bonds  Net conversion of one bond of the double bond to two single bonds


Properties of Alkene Reactions

Exothermic  Products are more stable (lower energy) than the reactants  Rate of reactions depends on the activation energy (some needs catalyst)


Hydrogenation
The reaction is carried out under pressure at a temperature of 200 C in the presence of a metallic catalyst.  Common industrial catalysts are based on platinum, nickel or palladium. For laboratory syntheses, Raney nickel (an alloy of nickel and aluminium) is often employed.


Hydrogenation

CH2=CH2 + H2 Ethylene

CH3-CH3 Ethane

Halogenation CH2=CH2 + Br2 BrCH2-CH2Br

Hydrohalogenation
Reactions of hydrogen halides (HX) with alkenes produces haloalkanes (alkyl halide)  Some reactions proceeds to regioselectivity


Regioselectivity
Was first noted by Vladimir Markovnikov  Regioselective reaction takes place when one direction of bond forming or breaking occurs in preference to all other directions.  The Markovnikovs Rule


Markovnikovs Rule


The rich get richer

In the addition of HX to an alkene, hydrogen adds to the doubly bonded carbon that has greater number of hydrogens already bonded to it; halogen adds to the other carbon.

Hydration
Addition of Water: Acid-catalyzed hydration  In the presence of an acid catalyst, most commonly conc. H2SO4, water adds to the carbon-carbon double bond to give an alcohol.


Hydration
In simple alkenes, hydration follows the Markovnikovs rule.  That is, H adds to the carbon of the double bond with the greater number of hydrogens and OH adds to the carbon with the smaller number of hydrogens.


Halogenation
Addition of bromine and chlorine  Br2 and Cl2 react with alkenes at room temperature by addition of halogen atoms to the carbon atoms of the double bonds


Halogenation


Generally carried out either by using pure reagents or by mixing them in an inert solvent, such as dichloromethane, CH2Cl2.

Importance
Useful qualitative test for the presence of an alkene.  How?: Br2 in CCl4 (red to brown) is mixed with a suspected alkene, the disappearance of the red color means that the bromine was added to the double bond.


Hydrogenation
Addition of Hydrogen  All alkenes react quantitatively with H2 in the presence of a transition metal catalyst to give alkanes.  Catalysts used are platinum, palladium, ruthenium and nickel.


Hydrogenation


It involves reduction by hydrogen in the presence of a catalyst, thus; it is also called as the catalytic reduction or catalytic hydrogenation.

Hydrogenation
Catalyst finely powdered solid  Carried out by dissolving alkene in ethanol or other non-reactive organic solvent, adding the catalyst, and exposing the mixture to hydrogen gas at pressures ranging from 1 to 150 atm.


Polymerization
Formation of chain-growth polymers  Most important reaction of alkenes  With the presence of initiators, many alkenes form polymers


Polymerization
Low-density Polyethylene (LDPE)  Transparent polymer from the ethylene polymerization with peroxide as initiator  Highly branched  Do not pack well together  London dispersion forces are weak


Polymerization
High-density Polyethylene (HDPE)  Does not rely on peroxide initiators  Developed by Karl Ziegler and Guilio Natta  Little chain branching  Chains are pack together more closely  Stronger london dispersion forces


Sample
2-methylpropene with HI  2-methylcyclopentene with HCl  Propene with HBr


Sample
   

 

Hydration of ethene with conc. H2SO4 Hydration of propene with conc. H2SO4 Hydration of 2-methylpropene with conc. H2SO4 Acid-catalyzed hydration of 1methylcyclohexene Acid-catalyzed hydration of 2-methyl-2-butene Acid-catalyzed hydration of 2-methyl-1-butene

Sample
Bromination of cyclopentene with CH2Cl2  Chlorination of 2-methylcyclohexene with CH2Cl2.  Bromination of 3,3-dimethylbutene with CH2Cl2


Sample
Catalytic reduction of trans-2-butene with Pd  Catalytic reduction of cis-2-butene with Pd  Catalytic hydrogenation of cyclohexene with Pd


Benzene and Its Derivatives

Benzene: Its Properties

Benzene is an organic chemical compound with the molecular formula C6H6.  It is sometimes abbreviated PhH. Benzene is a colorless and highly flammable liquid with a sweet smell and a relatively high melting point.


Benzene: Its Properties

Because it is a known carcinogen, its use as an additive in gasoline is now limited, but it is an important industrial solvent and precursor in the production of drugs, plastics, synthetic rubber, and dyes.  Benzene is a natural constituent of crude oil, and may be synthesized from other compounds present in petroleum.


Benzene: Its Properties

Benzene is an aromatic hydrocarbon  It is also related to the functional group arene which is a generalized structure of benzene.  Arene is use to describe aromatic hydrocarbon.


Benzene: Its Properties

A group derived from the removal of an H from a arene is called an aryl group (Ar-).  Discovered by Michael Faraday  Conflict arose between chemists because of the molecular formula


Benzene: Its Properties

Has few hydrogens for its six carbons (compare to hexane); chemists argued it to be unsaturated.  However, benzene does not behave like alkenes


Benzene: Its Structure

First structure was proposed by Friedrich August Kekul  Consist of six-membered ring with alternating single and double bonds, with one hydrogen bonded to each carbon


Benzene: Its Structure

Kekul proposal was consistent with many chemical properties of benzene  But was objected because it does not undergo reactions similar to alkenes.


Resonance Structure of Benzene



In answer to the objections to the structure proposed by Kekul, resonance hybrid of the molecular benzene was used.

Resonance Structure of Benzene



Experimentally, the length of the carboncarbon bond in benzene is not as long as a C-C nor as short as a C=C, but rather midway between the two.

Resonance Structure of Benzene



The closed loop of six electrons ( two from the second bond of each double bond) characteristic of a benzene ring is sometimes called an aromatic sextet.

Resonance Structure of Benzene



The benzene ring is greatly stabilized by resonance, which explains why it does not undergo the addition reactions of typical alkenes.

Nomenclature of Aromatic Hydrocarbons

Aromatic hydrocarbon is evident with the presence of a benzene ring.  Benzene has six carbon atoms are arranged in a ring with alternating double bonds.


Sample
       

Ethylbenzene Methylbenzene (toluene) Phenylethene (styrene) Hydroxybenzene (phenol) Anisole Aniline Benzaldehyde Benzoic acid

Nomenclature of Aromatic Hydrocarbons

The substituent group derived by loss of an H from benzene is called a phenyl group (Ph-).  In molecules containing other functional groups, phenyl groups are commonly assigned as substituents.


Sample
1-phenylcyclohexene  4-phenylbutene


Nomenclature of Aromatic Hydrocarbons

Monosubstituted benzenes are named by combining the substituents name with the word benzene.  For disubstituted benzenes the 3 possible isomers are named using the prefixes ortho, metha and para (o, m, p) to designate the 1,2- , 1,3- and 1,4 relationships of substituents on the benzene ring.


Sample
4-bromobenzoic acid (p-bromobenzoic acid)  3-chloroaniline (m-aniline)  1,3-dimetyhlbenzene (m-xylene or mdimethylbenzene)  1-chloro-4-ethylbenzene (pchloroethylbenzene)


Nomenclature of Aromatic Hydrocarbons

For three or more substituents, specify their locations by numbers (smallest set).  If one of the substituents imparts a special name, then name the molecule as a derivative of that parent molecule.


Sample
4-chloro-1-methyl-2-nitro benzene (4chloro-2-nitrotoluene)  2,4,6-tribromo-1-hydroxybenzene (2,4,6tribromophenol)  2-bromo-1-ethyl-4-nitrobenzene  1-methyl-2,4,6-trinitrobenzene (2,4,6trinitrotoluene or TNT)


Sample
m-iodotoluene  3,5-dibromobenzoic acid  P-chloroaniline


Polynuclear Aromatic Hydrocarbons (PAHs)

Molecules containing two or more benzene rings, with each pair of rings sharing two adjacent carbon atoms.  Naphthalene, anthracene, phenanthrene


Characteristic Reactions of Benzene

The most characteristic reaction of aromatic compounds is substitution at a ring carbon (aromatic substitution).  Halogenation  Nitration  Sulfonation


Halogenation


Cl2 and Br2 noramlly do not react with benzene but with an Fe catalyst, halogens reacts rapidly to give halobenzene and HCl.

Sample
Chlorination of benzene in FeCl3  Bromination of benzene in FeCl3


Nitration


Heating benzene or its derivative with conc. nitric acid, one of the hydrogen atoms bonded to the ring is replaced by a nitro (-NO2) group.

Sample
Nitration of benzene  Nitration of toluene


Sulfonation
Heating an aromatic compound with conc. sulfuric acid results in the formation of an arenesulfonic acid and water.  Major use is in the preparation of synthetic detergents


PHENOLS
The functional group of phenols is a hydroxy group bonded to a benzene ring  Subtituted phenols are named either as derivatives of phenols or by common names.


Sample
Phenol  3-methylphenol (m-cresol)  1,2-benzenediol


Sources
Widely distributed in nature  Phenol and the isomeric cresol (o-, m-, and p-) are found in coal tar.  Thymol and vanillin are important constituents of thyme and vanilla beans.  Urushiol is the main component of poison ivy an irritating oil


Acidity and Properties

Weak acids  Insoluble in water  Reacts with strong bases like NaOh and KOH forming water-soluble salts