“L’autor/L’autora s’acull a l’article 32 de la Llei de propietat intel·lectual vigent respecte de l’ús parcial

d’obres alienes com ara imatges, gràfics o altre material contingudes en les diferents diapositives,
donat el caràcter i la finalitat exclusivament docent i eminentment il·lustrativa de les explicacions a
classe d’aquesta presentació.”

“El autor/La autora se acoge al artículo 32 de la Ley de Propiedad Intelectual vigente respecto al uso
parcial de obras ajenas, como imágenes, gráficos u otro material contenido en las diferentes
diapositivas, dado el carácter y la finalidad exclusivamente docente y eminentemente ilustrativa de
las explicaciones en clase de esta presentación.“

UNIT 10
ALCOHOLS

1
UNIT 10 ALCOHOLS

10.1. Nomenclature.
10.2. Structure and physical properties.
10.3. Alcohols preparation.
10.4. Alcohols reactivity.

UNIT 10 Nomenclature

IUPAC: alkane Alkanol, OH position should be indicated (lowest locant)

Cycloalcanols

2
UNIT 10 Nomenclature

OH as substituent: hydroxy

Types of alcohols

Common Nomenclature:
MeOH: Methyl alcohol
EtOH: Ethyl alcohol
PhCH2OH: Benzylic alcohol

UNIT 10 Structure

Sp3 hybridization of the oxygen atom

OH bond shorter than CH bond

Homolytic cleavage of O-H bond easier than C-H

• DHoO-H = 104 kcal mol-1
• DHoC-H = 98 kcal mol-1

3
UNIT 10 Structure and physical properties

μ = 1.9 D μ = 1.7 D

0.96 A
R O Hydrogen bonds
R H R
O 2.07 A O···H-O ΔHo ~ 5-6 kcal mol-1
O
H H O O-H covalent ΔHo = 104 kcal mol-1
H R

The extended net of hydrogen bonds between neighbour alcohol

molecules difficult the removal of a molecule from the liquid surface

UNIT 10 Structure and physical properties

The alcohol –OH group is hydrophilic and therefore increases

the solubility in H2O (hydrogen bonds).

As the carbon chain becomes longer, it resembles more to an

alkane and then the solubility in H2O decreases.

4
UNIT 10 Acid-base properties

Keq= 1019.5

Keq 1

UNIT 10 Acid-base properties

ROH MeOH i-PrOH t-BuOH

pKa 15.5 17.1 18

Stonger acid pKa Weaker acid

MeOH; ROH primary; ROH secondary; ROH tertiary

The solvation of tertiary

alcohols is less effective

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UNIT 10 Acid-base properties

Alcohols can behave as acid or base

Very strong acid are required to

protonate alcohols

UNIT 10 Industrial preparation of ROH

Cu/ZnO
CO + 2 H 2 CH 3OH
CrO 3, 250 ºC
50 - 100 atm

6
UNIT 10 Alcohol synthesis

Nucleophilic substitution (SN1/ SN2)

Problems:
H 2O In SN1 carbocations are formed and
R1 R1
o H 2O/ OH they can rearrange or give E1.
R Br SN1/ SN2 R OH
–OH can give E2.

AcO- ion is less basic than -OH, therefore is better for the SN2

O
O
O Me OH
R Br R O Me R OH + AcO
SN2

UNIT 10 Alcohol synthesis

Alkenes hydration

1) Hg(OAc)2, H 2O
2) NaBH 4

1) B2H 6, THF
OH 2) H 2O2, NaOH OH
R R
R
antiMarkovnikov
Markovnikov H 2O, H

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UNIT 10 Alcohol synthesis

Carbonyl compounds reduction

Oxidation/Reduction in Organic Chemistry

UNIT 10 Alcohol synthesis

The carbonyl group is electrophilic and

can suffer an hydride ion (H-) addition

The oxygen of the carbonyl captures a proton of the solvent

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UNIT 10 Alcohol synthesis

NaBH4 is a weak redactor. Only reduces aldehydes and ketones.

A protic solvent is required to activate the carbonyl group

The resulting ethoxyborohydride “it can” transfer other 3 hydrides

UNIT 10 Alcohol synthesis

LiAlH4 is more reactive. Reduces all types of carbonyl compounds and it

must be used in aprotic solvents.

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UNIT 10 Alcohol synthesis

RCO2H 1) LiAlH 4 RCH 2OH

RCO2Me 2) H2O RCH2OH + MeOH

UNIT 10 Alcohol synthesis

Reaction of carbonyl compounds with organolithium or organomagnesium

reagents

10
UNIT 10 Alcohol synthesis

Reaction of carbonyl compounds with R-M

UNIT 10 R-M preparation

R-M preparation:
Reactivity: I > Br > Cl
THF
0 - 10 ºC
R-Br + 2 Li RLi + LiBr

11
UNIT 10 R-M structure

C-M: 40% iónico 35% iónico

The formation of RLi or RMgX are examples of inverted polarization

(umpolung). The electrophilic carbon of R-X turns to nucleophile

RM are strong bases in H2O (important the must be used in

absence of humidity).

UNIT 10 Alcohols reactivity

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UNIT 10 Alkoxides preparation

Alkoxides are useful compounds?

UNIT 10 Reaction with strong acids

Primary alkyloxonium ions react via SN2.

Chloroalkanes can not be obtained by this
method because Cl- is a poor nucleophile.

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UNIT 10 Reaction with strong acids

Tertiary alkohols gave carbocations that in the presence of good nucleophiles

can give SN1 at low temperatures.
Non nucleophilic acids, as H3PO4 and H2SO4, with high temperatures are
used to favour E1 in secondary and tertiary ROH

UNIT 10 Reaction with strong acids

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UNIT 10 Carbocation rearrangement

UNIT 10 Carbocation rearrangement

Hyperconjugation makes the C-H weaker and contributes to a

hydride shift faster than a SN1/E1 reaction

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UNIT 10 Carbocation rearrangement

Alkyl groups also can shift

Primary alcohols rearrange without forming a carbocation.

In this case, SN2 is sterically hindered and the methyl shift at the same
time than the H2O leaving the molecule

UNIT 10 Reaction with PX3

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UNIT 10 Reaction with PX3, PX5, POX3

In situ generation of PI3

PCl5 and POCl3 are used to prepare R-Cl.

Similar mechanism to the reaction with PBr3

UNIT 10 Reaction with SOCl2

Generally Et3N is added to neutralise the generated HCl

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UNIT 10 Generation of organic and inorganic esters

UNIT 10 Alkyl sulphonates

Alkyl sulphonates are crystalline solids that can be easily purified. They
react with a ample nucleophile scope.

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UNIT 10 Oxidation of alcohols with Cr (VI)

Tertiary alcohols are NOT oxidized with Cr (VI)

UNIT 10 Oxidation mechanism

E2

Cr (IV) disproportionate to Cr (III) and Cr (V) (also oxidant).

With CrO3 the mechanism is similar.

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UNIT 10 Primary ROH overoxidation

Aldehyde hydrides are easily oxidized

H OH
Cr (VI) H 2O
R OH R O R OH
CrO 3

OH OHOH
E2 O
R Cr
R O O O
H

O O O
Cr H
H
OH

UNIT 10 Oxidation of RCH2OH to RCHO

PCC and PDC are anhydrous organic solvent soluble Cr(VI) reagents
that are used to oxidize RCH2OH to RCHO.

Cl O
Cr
O O N
H
PCC

20