ALCOHOLS:  Functional group is the OH or hydroxyl group.  The hydroxyl group in alcohols is bonded to a sp3 carbon.

Types of alcohols:  Primary alcohol RCH2OH Ex. CH3CH2OH  Secondary alcohol R2CHOH Ex. CH3CHOHCH3  Tertiary alcohol R3COH Ex. (CH3)3COH Alcohols may also be classified based on the number of hydroxyl groups:  Monohydroxy alcohols contain only 1 hydroxyl group. Ex. CH3CH2OH ethanol  Polyhydroxy alcohol contains more than one hydroxyl group Ex. HO-CH2-CH2-OH 1,2-ethanediol Physical Properties of Alcohols:  Alcohols have higher boiling points compared to alkanes of similar MWs.  Boiling point increases with increasing chain length.  Polyhydroxy alcohols have higher boiling points than monohydroxy alcohols of similar MW.  Alcohols with low MW are soluble in water.  As chain length increases, solubility in water decreases.  Polyhydroxy alcohols are more soluble in water than their monohydroxy counterparts. PREPARATION OF ALCOHOLS:  Hydration of alkenes  Hydroboration of alkenes, followed by oxidation  Nucleophilic substitution of alkyl halides using OH or water as nucleophile  Reaction of Grignard reagents with ethylene oxide, aldehydes, ketones and esters  Oxidation of alkenes with cold, dilute, alkalinel KMnO4 or OsO4 (to form cis-1,2-diols) Alcohols as bases:  The unshared pair of electrons on oxygen makes alcohols behave as Lewis bases (electron pair donors). Alcohols as acids:  Alcohols can also act as Bronsted-Lowry acids (proton donors).  Alcohols are slightly weaker acids than water.  Alcohols are much stronger acids than terminal alkynes. Relative Acidity of Alcohols:  Relative acidities of alcohols (in solution): o o o 1 ROH > 2 ROH > 3 ROH  Presence of electron-donating substituents decreases acidity, while presence of electron-withdrawing groups increases acidity.  In solution, anything that interferes with H-bonding makes the alkoxide less stable.  Alkyl groups get in the way of H-bonding with solvent.  Alcohols with unbranched C atoms near the OH groups are stronger acids in solution. REACTIONS OF ALCOHOLS: A. Conversion to alkyl halides 1. Reaction with thionyl chloride (SOCl 2)

.. R O H ..

+ SOCl2

R Cl + SO2 + HCl
3RX + H3PO3

2. Reaction with phosphorus trihalide (PX3)

3ROH + PX3
3. Reaction with hydrogen halides

ROH + HX

RX + HOH

 Nucleophilic substitution reaction.  Reaction may proceed via SN1 or SN2, depending on the kind of alcohol (whether o o o 1 , 2 or 3 alcohol). o  1 ROH will react via SN2. o  3 ROH will react via SN1. Lucas Test: o o o  Distinguishes between 3 , 2 and 1 ROH.

R O H

+ HCl

ZnCl2

+ R O H Zn
+

R Cl
   

Cl

Reaction is SN1. Stability of carbocations: 3o > 2o > 1o The more stable the carbocation, the more easily it is formed. o o o Relative reaction rate: 3 > 2 > 1 ROH

Summary for the reaction of alcohols with hydrogen halides:  The reaction is catalyzed by acids. Even though the aqueous HX are acids, presence of additional H2SO4 speeds up formation of the alkyl halide. o  Rearrangement of the alkyl group occurs, except with most 1 ROH.  Order of reactivity of ROH toward HX: 3o > 2o > 1o > CH3OH B. Dehydration of alcohols:  Alcohols, when heated in acid, are converted to alkenes.  Follows Saytzeffs Rule: Elimination gives the more substituted alkene as the major product. C. Oxidation of alcohols 1. Using Cr2O72-, H2SO4:
H R C OH H 1o alcohol H R C OH R 2o alcohol R R C OH R 3o alcohol Cr2O7 , H2 SO4
-2

Cr2 O7 , H2 SO4

-2

O R C OH carboxylic acid

Cr2 O7 , H2 SO4

-2

O R C R ketone

No Reaction

2. Using KMnO4 in NaOH/H2O. RCH2 OH 1o alcohol KMnO4, NaOH, H2O O R C O carboxylate O R C R ketone
-

H3O

O R C OH

RCH OH R 2o alcohol

KMnO4, NaOH, H2O

3. Selective oxidation using PCC, pyridinium chlorochromate:

CrO3

+ HCl

+ N

+ N H

CrO3Cl

PCC

RCH2

OH

PCC

O R C H