Alcohols

Properties
Classification
Suffix e is changed to -ol Classification is based on the number of C-C Same as usual, meth is none, 1o is one, 2o is 2, 3o is three

Bonding Polarity
Polarity of OH molecule result sin slightly polarity about alcohols Obviously this will be diminished with size This polarity results in the existence of dipole-dipole interactions

Hydrogen Bonding
Hydrogen bonding exists due to OH HB occurs between OH molecules o This bonding is represented with dotted lines Obviously the structure affects how easily molecules can orientate to experience HB o This will affect the strength of the HB experienced

Strength of Bonding
Consider number of possible HB donators and acceptors o In water tonnes of possible acceptors and donators? Consider how easily HB can occur Larger molecules do become less polar, but they also gain size and hence increase in dispersion forces

MP/BP
Higher than similar sized hydrocarbons

Solubility
Very soluble in water due to the existence of hydrogen bonding Solubility is much greater than that of similar sized hydrocarbons

Acid/Base Behaviour
Alcohols can act as a weak acid or a weak base

Acidity Alcohols
Acidity of most alcohols is similar or less than that of water Therefore, pH (Alcohol water solution) = pH (Pure water) o Acidity isnt greatly affected by water? Acidity increases with decreasing molecular size of the alcohol

Phenols

 Phenols are benzene rings with OH functional group Acidity of phenols is significantly higher than that of alcohols PHENOLS WILL REACT WITH BASES TO FORM SALTS

Stability of Phenoxide Ion Increased acidity is due to the stability of the phenoxide ion o This stability occur due to the possible resonance structures o Possible resonance structures = Stability o This is why carboxylic acids are stronger than alcohols Increased stability of conjugate base results in increased acidity

Rule of Thumb for OH pKa

Compound Alkylsulfonates Carboxylic Acids Phenols Alcohols pKa 0 5 10 15

Separating Phenols and Alcohols

Separation is achieved by o First having both alcohol and phenol in an organic phase o Then an aqueous base solution is added o Only the phenol will react to form a salt o This allows the phenol to enter the aqueous layer The process is then reversed by adding more organic solvent to the aqueous solution, which causes the phenol to move into it, The process is then repeated to purify the phenol

Basicity
Presence of strong acids causes O atom of -OH to behave as a weak base o Strong acids such as sulphuric are needed Proton transfer from strong acid forms the oxonium ion
o Note: Oxonium ion allows for H2O to become a leaving group, this is important for alcohol reactions

Reactions
OH as a leaving group
It is important to remember that for all alcohol reactions, -OH is a bad leaving group

Reactions with Active Metals

Alcohols react with active metals to liberate H2 gas and form an alkoxide o Active metals include Li, Na, K etc

Alkoxides
Stronger bases than OH o Can be used as a base in elimination reactions Are good nucleophiles o Can act as a nucleophile in substitution reactions

ROH to RX (Nu Substitution) Theory

ROH to RX involves substitution of halogen for OH, at the saturated carbon o Occur via SN1 or SN2 mechanisms o Common reagents are HX and SOCl2 (thionyl chloride) But OH is a bad leaving group, and must be acidified (receive proton) to allow the formation of H 2O which is a much better leaving group

Conditions

1o and 2o Alcohols Require concentrated HBr or HI to form alkyl bromides/iodides o Will not react with HCl Water soluble 3o alcohols React rapidly with halogen acids (HX) It should be noted that 1o and 2o acids are unreactive in these conditions Water insoluble 3o alcohols React by bubbling gaseous HCl through solution of alcohol and diethyl ether or THF

1o/2o Alcohols (SN2)

Inversion of configuration Step 1: Proton transfer to OH to convert to H2O, a better leaving group

Step 2: Nu displacement of H2O by X This is the rate determining step

3o Alcohols (SN1)
Racemic product Step 1: Rapid, reversible acid-base reaction transfers proton to the OH group, creating H2O, a better leaving group Creates oxonium ion

Step 2: Loss of H2O gives carbocation intermediate This is the slow, rate determining step

Step 3: Reaction with halide ion completes the reaction

Factors
Factors are the same for any SN reaction o Steric o Electronic

Dehydration ( Elimination) Theory

Dehydration is removal of OH to form a double C=C, producing water These reactions need to have an acid catalyst o Obviously this catalyst is regenerated The mechanism is elimination o Hence Zaitsevs rules must be applied

Conditions
1o Alcohols Heated to high temperatures Require acid catalyst 2o Alcohols Lower temperatures than 1o Require acid catalyst o 3 Alcohols Temperatures slightly above room temperature Require acid catalyst

1o Alcohols (E2)
Zaitsevs Rule Step 1: Rapid, reversible acid-base reaction transfers proton to the OH group, creating oxonium ion, hence allowing for H2O to be a leaving group

Step 2: Proton transfer to solvent and loss of H2O This regenerates the acid catalyst

2o /3o Alcohols (E1)

Zaitsevs Rule Step 1: Rapid, reversible acid-base reaction transfers proton to the OH group, creating oxonium ion, hence allowing for H2O to be a leaving group

Step 2: Loss of H2O gives carbocation intermediate

 This is the slow, rate determining step

Step 3: Proton transfer from an adjacent carbon to H2O gives alkene Regenerates acid catalyst

Dehydration/Hydration
Acid catalysed hydration of an alkene and dehydrations are competing processes o Large amounts of water favour alcohol formation o Scarcity of water favour alkene formation

Oxidation
[O] is generic oxidant

1o Alcohols
Oxidised to aldehydes or carboxylic acids o Obviously this can occur due to the position of the OH The product depends on the [O] used Carboxylic Acid Formation Occurs when chromic acid is used

Aldehyde formation Occurs when PCC is used

2o Alcohols 3o Alcohols
Do not undergo oxidation