ALCOHOLS AND PHENOLS PHENOL DERIVATIVES

Alcohol- -OH (hydroxyl group) bonded to a tetrahedral
carbon atom
- HC derivatives that have a gen. formula of
R-OH, (-OH) represents major functional group
1. Butylated Hydroxyl Anisole (BHA)
- for preservation of meat products
2. Butylated Hydroxyl Toluene (BHT)
- for animal feeds and vegetable oils
- rancid- unpleasant odor of spoiled fat

3. Thymol
- for medicine to kill fungi and hookworms

PHYSICAL PROPERTIES OF ALCOHOLS AND PHENOLS

# of C atoms = Molecular weight

Molecular weight = BP
Molecular weight = Solubility in water

COMMONLY ENCOUNTERED ALCOHOLS Hydrogen Bonding

- because of the large difference in electron negativity
A. Methanol-methyl alcohol, wood alcohol, wood spirit between O and H, -OH bonds alcohols are polar covalent
- solvent used for paints, varnishes and adhesives
- not safe for ingestion Solubility
- liver (methanol-> formaldehyde-> formic acid) - alcohol molecules have both polar and non-polar
formalin – toxic substance characters
- alcohols are semi-polar
B. Ethanol-ethyl alcohol, grain alcohol, drinking alcohol
CH3-CH2-CH2-OH
- present in alcoholic beverages
- can be produced by yeast fermentation of sugars 3 C and below (short chain alcohols) – miscible
found in grains like corn, rice, barley 4 C and above (long chain alcohols) – immiscible
- acetaldehyde-> acetic acid
Hydrogen Bonding of Alcohols
Health problems:
 Alcohols can hydrogen-bond to water
- liver cirrhosis
- addiction  Alcohols can hydrogen-bond to each other
- memory loss
- birth defects Boiling Point
- because alcohols hydrogen bond to each other, they
C. 2- Propanol- isopropyl alcohol, rubbing alcohol (70% have higher boiling points than alkanes of the same MW
isopropyl alcohol sol’n)
- helps to lower fever Name Structure MW BP
- solvent for perfumes, cosmetics and skin creams propane CH3CH2CH3 44.09 g/mol -42.1°C
dimethyl ether CH3OCH3 46.07 g/mol -24 °C
ethanol CH3CH2OH 46.07 g/mol 78.3 °C

REACTIONS OF ALCOHOLS AND PHENOLS

1. Acid-Base Reactions
- alcohols have same pKa value as water, aqueous sol’n
of alcohols have approximately the same pH as pure
water
- phenols are weak acids and react with aqueous sodium
hydroxide to form water soluble salts

Phenol- aromatic, org. compound in which -OH grp is

attached to a C that is part of an aromatic ring
- gen. formula: Ar-OH
phenol phenoxide ion
2. Oxidation Reaction (Dehydrogenation)
- occurs when molecule loses electrons
C-O C-H
- oxidizing agents: potassium permanganate in either
acidic or basic sol’n (KMnO4/H or KMnO4/OH) and
potassium dichromate in acidic sol’n (K2Cr2O7/H)
- product of alcohol oxidation depends on whether the
starting alcohol is a primary, sec or tert alcohol
TESTS TO DIFFERENTIATE ALCOHOLS AND PHENOLS
1. Lucas Test
- differentiate primary, sec, tert alcohols using anhydrous
ZnCl2 in concentrated HCl
- nucleophilic substitution rxn (SN1)

Primary- oxidized first to aldehydes then carboxylic acid

*oxidation of ethanol to acetaldehyde happens in the

liver that is further oxidized to acetyl coenzyme A (then
acetic acid), used to synthesize fat or eventually be
oxidized to H2O and CO2

Secondary- oxidized to ketones only

2. Ferric Chloride Test
- qualitative colorimetric test for phenols
- forms blue, violet, purple, green, or red-brown upon
addition of aqueous ferric chloride reagent
- yellow-orange is negative

General Equation
3ArOH + FeCl3 → Fe(OAr)3 + 3HCl
Tertiary- absence of H on the alpha C, no oxidation Ferric phenoxide- colored

DATA AND RESULTS

A1. Solubility in Water
Methyl alcohol Miscible
Ethyl alcohol Miscible
Phenols- oxidized to quinones Propyl alcohol Miscible
N-butyl alcohol Immiscible
Oxidizing agent catalyst
N-amyl alcohol Immiscible
Phenol Miscible
KMnO4
A2. pH Reaction
Methyl alcohol 7 (6-7)
Ethyl alcohol 7 (6-7)
Propyl alcohol 7 (6-7)
N-butyl alcohol 7 (6-7)
3. Esterification
N-amyl alcohol 7 (6-7)
- chemical rxn between a carboxylic acid and an alcohol
where esters are obtained Phenol 5 to 6
- rxn takes place in acidic environments
- favors alcohols than phenols B. Lucas Test
Lucas reagent: anhydrous ZnCl2 in HCl
Positive result: formation of turbidity or layer formation

R
 Compound Visible Reactivity Products *Many of alcohols properties depend upon:
Result - unsaturated nature: oxidation to
N-butyl Turbidity Least 1-chlorobutane ketone/aldehyde/acid
alcohol in high reactive - weaker R-O bond and its ability to easily break and
temp. form an R+ cation (this makes it a good participant in
2- butyl Turbidity More 2- chlorobutane SN1 rxn)
alcohol after 5-10 reactive
minutes - Phenols cannot be oxidized at the -OH to form a
3- butyl Immediate Most 2-chloro-2- ketone/acid
alcohol turbidity reactive methylpropane - Phenylic carbocations are unstable, thus SN1 rxn
Phenol No Non- reactive doesn’t happen and the Ph-O bond stays put
turbidity
*Most of the rxn of phenol depend on:
C. Oxidation
- aromatic phenyl ring
Oxidizing agent: KMnO4
- weaker O-H bond
Positive result: Decolorization with brown ppt

Compound Visible Result Interpret Product

N-butyl Decolorization Oxidized Butanal
alcohol / Brown ppt Butanoic acid
2- butyl Decolorization Oxidized Butanone
alcohol / Brown ppt
3- butyl None Not None
alcohol oxidized
Phenol Decolorization Oxidized Quinones
/ Brown ppt

D. Ferric Chloride Test

Reagent: 2% FeCl3
Positive result: blue, violet, red or green solution

N-butyl alcohol Yellow-orange Negative

sol’n
Phenol Violet/purple Positive
sol’n

E. Esterification
Reactants: Alcohol + Salicylic acid
Product formed: Ester
Positive result: Distinct fragrant odor

Methanol Mint odor Methyl salicylate

Phenol Paste odor Phenyl salicylate

*Why do phenols react differently from alcohols

despite the presence of same functional grp?

The difference in their structure account for some of

the differences they have. Alcohols consist of an -OH
grp bonded to a saturated carbon (sp3 hybridized, no
multiple bonds) while phenols consist of -OH bonded
to unsaturated sp2 carbon