Alcohols, Ethers, and Thiols

2011

Structure - Alcohols
The functional group of an alcohol is an -OH group bonded to an sp3 hybridized carbon
bond angles about the hydroxyl oxygen atom are approximately 109.5

Oxygen is also sp3 hybridized

two sp3 hybrid orbitals form sigma bonds to carbon and hydrogen the remaining two sp3 hybrid orbitals each contain an unshared pair of electrons

Structure - Ethers
The functional group of an ether is an oxygen atom bonded to two carbon atoms Oxygen is sp3 hybridized with bond angles of approximately 109.5. In dimethyl ether, the C-O-C bond angle is 110.3
H

H O

C H

C H

Structure - Thiols
The functional group of a thiol is an -SH (sulfhydryl) group bonded to an sp3 hybridized carbon The bond angle about sulfur in methanethiol is 100.3, which indicates that there is considerably more p character to the bonding orbitals of divalent sulfur than there is to oxygen

Nomenclature-Alcohols
IUPAC names
the longest chain that contains the -OH group is taken as the parent.
the parent chain is numbered to give the -OH

group the lowest possible number the suffix -e is changed to -ol

Common names
the alkyl group bonded to oxygen is named followed by the word alcohol

OH CH3 CH 2 CH 2 OH 1-Propanol (Propyl alcohol) CH 3 CHCH 3 2-Propanol (Isopropyl alcohol) CH3 CH2 CH2 CH 2 OH 1-Butanol (Butyl alcohol) CH3 OH CH3 CH 2 CHCH3 2-Butanol (sec-Butyl alcohol) CH 3 CH 3 CHCH 2 OH 2-Methyl-1-propanol (Isobutyl alcohol) CH 3 COH CH3 2-Methyl-2-propanol (tert-Butyl alcohol)

CH 2 CH 2 HO OH 1,2-Ethanediol (Ethylene glycol) CH 3 CHCH 2 HO OH 1,2-Propanediol (Propylene glycol) CH 2 CHCH 2 HO HO OH 1,2,3-Propanetriol (Glycerol, Glycerin)

 Unsaturated alcohols
the double bond is shown by the infix -en the hydroxyl group is shown by the suffix -ol number the chain to give OH the lower number
1 2 3 4 5 6

HOCH2 CH 2

CH2 CH 3

C C H H trans -3-Hexen-1-ol

Exercise: Write IUPAC names of the alcohols below

CH 3 OH (b) CH3 CH 2 OH (c) CH 3 ( CH 2 ) 6 CH 2 OH (d) H3 C C CH 2 CH 3 H OH (a) CH 3 CHCH 2 CHCH 3

Nomenclature - Ethers
IUPAC: the longest carbon chain is the parent. Name the OR group as an alkoxy substituent Common names: name the groups attached to oxygen followed by the word ether
CH 3 CH 2 OCH 2 CH 3 Ethoxyethane (Diethyl ether) CH 3 CH3 OCCH 3 CH 3 2-Methoxy-2-methylpropane (methyl tert -butyl ether, MTBE) OCH 2 CH 3 trans -2-Ethoxycyclohexanol OH

Nomenclature-thiols
IUPAC names:
the parent is the longest chain that contains the SH group change the suffix -e to -thiol

Common names:
name the alkyl group bonded to sulfur followed by the word mercaptan
SH CH3 CH 2 CH2 CH 2 SH 1-Butanethiol (Butyl mercaptan) CH3 CH2 CHCH3 2-Butanethiol (sec-Butyl mercaptan)

Physical Prop - Alcohols

Alcohols are polar compounds
H + C H H H O +

Alcohols are associated in the liquid state by hydrogen bonding

Physical Prop - Ethers

Ethers are polar molecules;
the difference in electronegativity between oxygen

(3.5) and carbon (2.5) is 1.0 each C-O bond is polar covalent oxygen bears a partial negative charge and each carbon a partial positive charge

Ethers are polar molecules, but because of steric hindrance, only weak attractive forces exist between their molecules in the pure liquid state Ethers hydrogen bond with H2O and are more soluble in H2O than are hydrocarbons

Physical Prop - Thiols

Low-molecular-weight thiols have a STENCH
the scent of skunks is due primarily to these two thiols . CH3
CH 3 CHCH 2 CH 2 SH 3-Methyl-1-butanethiol CH3 CH= CH CH 2 SH 2-Butene-1-thiol

The difference in electronegativity between S (2.5) and H (2.1) is 0.4. Because of the low polarity of the S-H bond, thiols
show little association by hydrogen bonding have lower boiling points and are less soluble in water

than alcohols of comparable MW

Acidity of alcohols
In dilute aqueous solution, alcohols are weakly acidic
CH3 O-H + O H H Ka = [CH 3 O - ] [H [CH 3 OH]
+ O ] 3

CH3 O

+ + H O H H

= 15.5

Basicity of alcohols
In the presence of strong acids, the oxygen atom of an alcohol behaves as a weak base
proton transfer from the strong acid forms an oxonium ion
CH3

O A base

H + H

+ H2 SO 4 O H

H An acid CH3

+ O H +

O H

H An oxonium ion

Reaction with Metals

Alcohols react with Li, Na, K, and other active metals to liberate hydrogen gas and form metal alkoxides
2 CH 3 OH + Methanol 2 Na 2 CH 3 O - Na + Sodium methoxide
+

H2

Conversion of alcoholo to alkyl halide

Conversion of an alcohol to an alkyl halide involves substitution of halogen for -OH at a saturated carbon
the most common reagents for this purpose are

the halogen acids, HX, and thionyl chloride, SOCl2

Water-soluble 3 alcohols react very rapidly with HCl, HBr, and HI. Low-molecular-weight 1 and 2 alcohols are unreactive under these conditions

CH 3 CH 3 COH + CH 3 2-Methyl-2propanol

HCl

25C

CH 3 CH 3 CCl + CH 3 2-Chloro-2methylpropane

H2 O

1 and 2 alcohols require concentrated HBr and HI to form alkyl bromides and iodides
CH3 CH 2 CH 2 CH 2 OH 1-Butanol
+

HBr

H2 O reflux
+

CH3 CH 2 CH 2 CH 2 Br 1-Bromobutane

H2 O

Dehdration of ROH
An alcohol can be converted to an alkene by elimination of H and OH from adjacent carbons (a b-elimination)
1 alcohols must be heated at high temperature in

the presence of an acid catalyst, such as H2SO4 or H3PO4 2 alcohols undergo dehydration at somewhat lower temperatures 3 alcohols often require temperatures only at or slightly above room temperature

CH 3 CH 2 OH OH

H2 SO 4 180 C H2 SO 4 140o C
o

CH 2 =CH 2 + H 2 O

+ H 2O Cyclohexene

Cyclohexanol

CH3 CH 3 COH CH3

H2 SO 4 50 C
o

CH 3 CH 3 C= CH 2 + H2 O 2-Methylpropene (Isobutylene)

Dehdration of ROH
Where isomeric alkenes are possible, the alkene having the greater number of substituents on the double bond generally predominates (Zaitsev rule)
OH CH 3 CH 2 CHCH3 2-Butanol 85% H 3PO4 heat CH 3 CH= CH CH 3 + CH 3 CH 2 CH= CH2 2-Butene 1-Butene (80%) (20%)

Mechanism of dehydration
1. Step 1: proton transfer from H3O+ to the -OH group to form an oxonium ion
HO

CH 3 CHCH 2 CH 3 + H

+ O H H H

rapid and reversible

+ H O

CH 3 CHCH 2 CH3 + An oxonium ion

O H H

Mechanism of dehydration
- Step 2: the C-O bond is broken and water is lost, giving a carbocation intermediate
+ H O

CH 3 CHCH 2 CH 3

slow and rate limiting + CH3 CHCH 2 CH3 A 2 o carbocation + H2 O

Mechanism of dehydration
Step 3: proton transfer of H+ from a carbon

adjacent to the positively charged carbon to water. The sigma electrons of the C-H bond become the pi electrons of the carbon-carbon double bond
H + CH 3 - CH - CH - CH 3 +

rapid

H CH 3 - CH = CH - CH 3 + + H O H

Oxidation of alcohol
A primary alcohol can be oxidized to an aldehyde or a carboxylic acid, depending on the oxidizing agent and experimental conditions
OH CH 3 -CH 2 A primary alcohol [O] O CH 3 -C- H An aldehyde [O] O CH 3 -C- OH A carboxylic acid

Oxidation of alcohol
Oxidation of 1-octanol by chromic acid gives octanoic acid
the aldehyde intermediate is not isolated
CrO3 CH 3 ( CH 2 ) 6 CH 2 OH H2 SO4 , H 2 O 1-Octanol O CH 3 ( CH 2 ) 6 CH Octanal (not isolated) O CH3 ( CH2 ) 6 COH Octanoic acid

Oxidation of alcohol
PCC oxidation of a 1 alcohol to an aldehyde
O CH 2 OH PCC CH

Geraniol

Geranial

Pyridinium chlorochromate (PCC): a form of Cr(VI) prepared by dissolving CrO3 in aqueous HCl and adding pyridine to precipitate PCC.

Oxidation of alcohol
2 alcohols are oxidized to ketones by both chromic acid and and PCC
CH(CH 3 ) 2 OH H2 CrO 4 acetone CH(CH 3 ) 2 O

CH 3 2-Isopropyl-5-methylcyclohexanol (Menthol)

CH 3 2-Isopropyl-5-methylcyclohexanone (Menthone)

Reaction of Ethers
Ethers, R-O-R, resemble hydrocarbons in their resistance to chemical reaction
they do not react with strong oxidizing agents such as

chromic acid, H2CrO4 they are not affected by most acids and bases at moderate temperatures

Because of their good solvent properties and general inertness to chemical reaction, ethers are excellent solvents in which to carry out organic reactions

Cleavage by Strong acids

Reaction of Thiols
Thiols are stronger acids than alcohols
CH3 CH 2 SH + H2 O pK a = 8.5
pK a = 15.9 CH 3 CH 2 OH + H 2 O

CH 3 CH2 S

+ H 3 O+
+

CH 3 CH 2 O + H 3 O

When dissolved an aqueous NaOH, they are converted completely to alkylsulfide salts

CH3 CH2 SH + Na + OHpKa = 8.5 Stronger Stronger + acid base CH3 CH 2 S Na + H2 O pKa = 15.7 Weaker base Weaker acid

Thiols are oxidized to disulfides by a variety of oxidizing agents, including O2.

they are so susceptible to this oxidation that they

must be protected from air during storage

+
1 2

2 RSH A thiol

O2

RSSR + A disulfide

H2 O