ALCOHOLS AND ALKYL HALIDES

INTRODUCTION
IUPAC NOMENCLATURE OF ALKYL
HALIDES
IUPAC NOMENCLATURE OF ALCOHOLS
CLASSES OF ALCOHOLS AND ALKYL
HALIDES
PHYSICAL PROPERTIES OF ALCOHOLS AND
ALKYL HALIDES: INTERMOLECULAR FORCES
Induced-dipole/induced-dipole forces are the only intermolecular attractive forces
available to nonpolar molecules such as alkanes and are important in polar molecules
as well. In addition, polar molecules also engage in dipole–dipole and
dipole/induced-dipole attractions. The dipole–dipole attractive force is easiest to
visualize and is illustrated in Figure 4.3 .
The most striking difference, however, is that despite the similarity in their dipole
moments, ethanol has a much higher boiling point than fluoroethane. This suggests that
the attractive forces in ethanol are unusually strong. They are an example of a
special type of dipole–dipole attraction called hydrogen bonding and involve, in this
case, the positively polarized proton of the —OH group of one ethanol molecule with
the negatively polarized oxygen of another. The oxygen of the —OH group of
alcohols serves as a hydrogen bond acceptor, while the hydrogen attached to the
oxygen serves as a hydrogen bond donor. Having both hydrogen bond acceptor and
donor capability in the same molecule creates a strong network among ethanol
molecules in the liquid phase .
Table 4.2 lists the boiling points of some representative alkyl halides and alcohols.
When comparing the boiling points of related compounds as a function of the alkyl
group, we find that the boiling point increases with the number of carbon atoms, as it
does with alkanes.
The importance of hydrogen bonding in alcohols is evident in the last column of the
table where it can be seen that the boiling points of alcohols are consistently higher
than the corresponding alkyl fluoride, chloride, or bromide.
Among alkyl halides, the boiling point increases with increasing size of the halogen;
alkyl fluorides have the lowest boiling points, alkyl iodides the highest. Dispersion
forces are mainly responsible. Induced-dipole/induced-dipole attractions are
favored when the electron cloud around an atom is easily distorted. This property of
an atom is its polarizability and is more pronounced when the electrons are farther
from the nucleus (iodine) than when they are closer (fluorine). Thus, induced-
dipole/induced-dipole attractions are strongest in alkyl iodides, weakest in alkyl
fluorides, and the boiling points of alkyl halides reflect this. The boiling points of the
chlorinated derivatives of methane increase with the number of chlorine atoms
because the induced-dipole/induced-dipole attractive forces increase with each
replacement of hydrogen by chlorine.
Thus, although the difluoride CH 3 CHF 2 boils at a higher temperature than CH 3 CH
2 F, the trifluoride CH 3 CF 3 boils at a lower temperature than either of them.
Even more striking is the observation that the hexafluoride CF 3 CF 3 is the lowest
boiling of any of the fluorinated derivatives of ethane.
The boiling point of CF 3 CF 3 is, in fact, only 11C higher than that of ethane itself.
The reason for this behavior has to do with the very low polarizability of fluorine and
a decrease in induced-dipole/induced-dipole forces that accompanies the
incorporation of fluorine substituents into a molecule.
SOLUBILITY IN WATER
Alkyl halides and alcohols differ markedly from one another in their solubility in
water. All alkyl halides are insoluble in water, but low-molecularweight alcohols
(methyl, ethyl, n -propyl, and isopropyl) are soluble in water in all proportions. Their
ability to participate in intermolecular hydrogen bonding not only affects the boiling
points of alcohols, but also enhances their water solubility. Hydrogen-bonded
networks of the type shown in Figure 4.5 , in which alcohol and water molecules
associate with one another, replace the alcohol–alcohol and water–water hydrogen-
bonded networks present in the pure substances.
Higher alcohols become more “hydrocarbon-like” and less water-soluble. 1-Octanol,
for example, dissolves to the extent of only 1 mL in 2000 mL of water. As the alkyl
chain gets longer, the hydrophobic effect (Section 2.17) becomes more important, to
the point that it, more than hydrogen bonding, governs the solubility of alcohols.
PREPARATION OF ALKYL HALIDES
1. Halogenation of alkanes
2. Addition of halogen acids to alkenes
3. Addition of halogen acids to alcohols
4. Action of thionyl chloride on alcohols
5. Halogen exchange reaction
HALOGENATION OF ALKANES
ADDITION OF HALOGEN ACIDS TO ALKENES
PREPARATION OF ALKYL HALIDES FROM
ALCOHOLS AND HYDROGEN HALIDES
The order of reactivity of the hydrogen halides parallels their acidity: HI > HBr > HCl
>> HF.
DIFFERENCE
FOR
PRIMARY
ALCOHOLS
OTHER METHODS FOR CONVERTING
ALCOHOLS TO ALKYL HALIDES
REACTIONS
SN1 unimolecular nucleophilic attack
SN2 bimolecular nucleophilic attack

More the steric hindrance decreased SN2 reactivity.

As a result, Tertiary alkyl halide will undergo SN1 reaction.
SUBSTITUTION REACTION
Reaction with aqueous KOH (Produces alcohol)
Reaction with sodium alkoxides (produces ether)
Reaction with ammonia (produces amines)
Reaction with sodium cyanide (produces alkyl cyanide)
Reaction with acetylides (produces alkynes)
ELIMINATION REACTIONS
Reaction with alcoholic KOH (produces alkenes)
Reduction (produces alkanes)
Reaction with Mg (Grignard reagent)
Reaction with lithium (alkyllithium)
Wurtz reaction (alkanes)
Halogenation
Friedal crafts alkylation (alkylbenzenes)
FRIEDAL CRAFTS ALKYLATION (ALKYLBENZENES)
PREPARATION OF ALCOHOLS
Hydrolysis of alkyl halides
Hydration of alkenes
Hydrolysis of esters
Reduction of aldehydes and ketones
Addition of Grignard reagent to aldehyde and ketones
HYDROLYSIS OF ESTERS
Ester hydrolysis is the most studied and best understood of all nucleophilic
acyl substitutions.
Esters are fairly stable in neutral aqueous media but are cleaved when
heated with water in the presence of strong acids or bases.
REDUCTION OF ALDEHYDES AND KETONES
Two points are especially important about this process.
ADDITION OF GRIGNARD REAGENT TO ALDEHYDE AND
KETONES
REACTIONS
With hydrogen halides (produces alkyl halides)
With thionyl chloride (alkyl chloride)
With phosphorus tribromide (alkyl bromide)
Acid catalyzed dehydration (alkenes)
CONVERSION OF ALCOHOLS TO ETHERS
ESTERIFICATION
OXIDATION OF ALCOHOLS
OXIDATION OF ALDEHYDE
TESTS FOR OH GROUP (FROM TEXTBOOK OF
ORGANIC CHEMISTRY BY BS BAHL)
Reaction with Sodium metal
Reaction with phosphorus pentachloride
HOW TO DISTINGUISH BETWEEN PRIMARY, SECONDARY
AND TERTIARY ALCOHOL (FROM TEXTBOOK OF
ORGANIC CHEMISTRY BY BS BAHL)
Lucas test (rate of reaction)
Dichromate test