Reactions of alcohols

With dehydrating agents

Alcohols reacts with concentrated sulphuric acid, heat under reflux at 170oC and eliminate a water molecule. Concentrated H3PO4 at 70oC and anhydrous Al2O3 at 600K can also be used as dehydrating agents. Alcohols can be converted to alkenes by a single step. This is elimination.

Reactions with halogenating agents

Reaction with PCL5(s)
C2H5OH(l) + PCl5(s) room temp dry condition C2H5Cl(g) + POCl3(l) + HCl(g)
1-chloroethane fumes

Reaction with PX3 (l) (X=Cl. Br, I)

Alcohols react with PCL3 or PBr3 or PI3 and form haloalkane. PCL (l)/rtp
3

PBr3 (l)/heat under reflux

PI3 (l)/heat under reflux

 Moist red phosporus and liquid bromine

+ moist red P/Br2(l)

CH3CH2Br

CH3CHOHCH3

+ moist red P/Br2(l)

CH3CHBrCH3

 Alcohols react with moist red phosphorus and liquid bromine, heating under reflux and produce bromoalkanes. In the reaction, moist red phosphorus react with Br2 (l) and form phosphorus tri bromide (PBr3), which reacts with alcohol. 3Br2 +2P (s) 2PBr3(l) PBr3 (l) + 3CH3CH2OH 3CH3CH2Br +H3PO3

Reaction with alkali iodine

Primary and secondary alcohols which contain CH3-C(OH)H- react with alkali iodine under warming and results yellow ppt of triiodomethane (CHI3). Aldehydes and ketone with CH3-CO- group can also give positive results for this reactions. Alkali iodine acts as an oxidizing agent. Tertiary alcohols which contain CH3-C(OH)group cannot be oxidized by alkali iodine

 Reagent: aq iodine and aq sodium hydroixde Condition: warm Type of reaction: oxidation Primary alcohol CH3-CH2-OH + 4I2(aq) + 6NaOH(aq) CHI3 (S) + HCOO-Na+ + 5NaI +5H2O Ethanol warm yellow ppt secondary alcohol CH3-CH(OH)-CH2CH3 + 4I2(aq) + 6NaOH(aq) Butan-2-ol

CHI3 (S) + HCOO-Na+ + 5NaI +5H2O

Tertiary alcohol (CH3)COH + I2(aq) + NaOH(aq) no reaction 2-methylpropan-2-ol warm Though CH3-C(OH) H group is present in some tertiary alcohols they cannot be oxidized by using I2 in NaOH or H2SO4 or dil H2SO4 & KMNO4. this is because C-H bond is absent on the carbinol carbon of tertiary alcohol. In tertairy alcohols carbinol carbon has three C-C bonds, which are stronger than C-H bond in primary and secondary alcohols. The oxidizing agent mentioned above are not strong enough to oxidize the C-C bond, but they can oxidize C-H bond easily in primary and secondary alcohols.

Esterification

Catalyst: concentrated H2SO4 (dehydrating agent - it removes water causing the equilibrium to move to the right and increases the yield Conditions: reflux

Uses of esters

Esters are fairly unreactive but that doesnt make them useless Used as flavourings

Naming esters

Named from the alcohol and carboxylic acid which made them... CH3OH + CH3COOH
from ethanoic acid

CH3COOCH3 + H2O
from methanol

CH3COOCH3

METHYL ETHANOATE