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Structurally, alcohols and phenols may be viewed as organic derivatives of water. General formula: R-OH Functional group -OH (hydroxyl group) alcohol : R = alkyl phenol : Ar = aromatic ring
CLASSIFICATION OF ALCOHOLS
Primary ROH: Carbon (carbinol carbon) with OH is bonded to one other carbon. Secondary ROH: Carbon with OH is bonded to two other carbons.
Tertiary ROH:
Carbon with OH is bonded to three other carbons. Aromatic alcohol or phenol: -OH is bonded to a benzene ring.
IUPAC NOMENCLATURE/NAMES
1. Name the longest carbon chain containing the OH group. Change e (alkane) to ol. 2. Number the carbon chain to give the OH group the lowest number. ( The hydroxyl group takes precedence over double/triple bonds) 3. Name all the substituents and give their numbers, as you would for an alkane/alkene
UNSATURATED ALCOHOLS
Priority goes to the hydroxyl group; assign that carbon the lowest number.
OH
Cl
1-chloro-3-ethylpent-1-en-4-yn-3-ol
NAMING PRIORITY
1. Acids
2.
3. 4. 5. 6.
Esters
Aldehydes Ketones Alcohols Amines
7.
Alkenes
8.
9.
Alkynes
Alkanes
10. Ethers
11. Halides
HYDROXY SUBSTITUENT
When -OH is part of a higher priority class of compound, it is named as hydroxy.
O
HO O
OH
C H 2O H
4-hydroxybutanoic acid
2-hydroxymethylcyclohexanone
NAMING DIOLS
Two numbers are needed to locate the two OH groups.
Use -diol as suffix instead of -ol.
HO OH
hexane-1,6-diol or 1,6-hexanediol
Glycols
1, 2 diols (vicinal diols) are called glycols. Common names for glycols use the name of the alkene from which they were made.
OH
NAMING PHENOLS
OH group is assumed to be on carbon 1. For common names of disubstituted phenols, use ortho- for 1,2; meta- for 1,3; and para- for 1,4.
OH
phenol
OH
OH
PHYSICAL PROPERTIES
Unusually high boiling points due to hydrogen bonding between molecules. Small alcohols are miscible in water, but solubility decreases as the size of the alkyl group increases; why??? alkyl group is hydrophobic.
BOILING POINTS
In increasing order:
Propane < dimethyl ether < ethanol
Q: Place the following compounds in decreasing order of boiling points and account for the order. 1-pentanol, 2-methyl-2-butanol, (A) (B) 3-methyl-2-butanol (C)
Answer
A>C>B As branching increases, the shape becomes more compact and spherical. There is less surface contact available for Van der Waals attractive forces between molecules hence lowering the boiling points.
SOLUBILITY IN WATER
Q: Arrange the following alcohols in decreasing order of solubility in water. Explain your answer. 1-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol (A) (B) (C)
Answer
C>B>A Alcohols with branched alkyl groups are more soluble in water than alcohols with nonbranched alkyl groups with the same number of carbons because branching minimizes the contact surface of the nonpolar portion of the molecule.
The longer the carbon chain The higher the boiling point Due to the increased Van der Waals attractive forces between molecules. The lower the water solubility Because the non-polar part is getting longer and hence a smaller proportion of the molecule is interacting in the water.
The more spherical (branched) the molecules, the less surface area it has. Lower boiling point than other isomeric alcohol Less Van der Waals attractive forces between molecules itself. More soluble in water The non-polar surface area is minimized.
ROH + H2O
RO-
+ H3O+
+ [ H O ] [ R O ] K = 3 a
[ R O H ]
Ka= acid-dissociation constant
CH2ClCH2OH + H2O
Phenol (pKa=10.0) is 100 million times more acidic than cyclohexanol (pKa=18.0). Why??? pKa ----- acidity
Phenols react with NaOH solutions (but alcohols do not), forming salts that are soluble in dilute aqueous solution.
Phenoxide ion is more stable; delocalization of the ve charge via resonance around the benzene ring make it stable; hence increase the acidity.
n o r e s o n a n c e
Acidity of Phenols
Effect of electron-withdrawing groups:
p-nitrophenol (pKa= 7.6) is almost 1000 times more acidic than phenol itself. Why???
N O O O
N O O
N O O
N O O
N O
Further delocalisation of ve charge of the phenoxide ion to the oxygen of the nitro group
Q:
Electron-withdrawing substituents make the phenol more acidic by stabilizing the phenoxide anion
Electron-donating substituents make the phenol less acidic by destabilizing the anion