Chemistry, 6th Edition

Organic Chemistry
L. G. Wade, Jr.

Capítulo 10
Estructura y Síntesis de
Alcoholes

Jo Blackburn
Richland College
College, Dallas
Dallas, TX
Dallas County Community College District
© 2006, Prentice Hall
 E t
Estructura
t d Alcoholes
de Al h l

• Grupo Funcional: (-OH) Hidroxilo

• Oxígeno es sp3
=>
Chapter 10 2
 Clasificación

• 1rio.: C enlazado al –OH está enlazado sólo a otro C.

• 2rio.: C enlazado al –OH está enlazado sólo a dos C.

• 3rio.: C enlazado al –OH está enlazado sólo a tres C.

• Aromáticos (fenoles): -OH está enlazado a un anillo de

benceno.
=>
Chapter 10 3
 Clasifique
CH3 CH3
CH3 CH CH2OH CH3 C OH
CH3

OH OH
CH3
C CH C
C CH2C
CH3 =>

Chapter 10 4
 Nomenclatura IUPAC
• Cadena más larga con el grupo -OH.

• Substituir terminación –ano

ano del alcano
por -ol.

• Enumerar la cadena por el extremo más

cercano all -OH.
OH
=>
Chapter 10 5
 Ejemplos
CH3
OH
CH3 CH CH2OH
CH3 CH CH2CH3
2-metil-1-propanol 2-butanol

OH
CH3
CH3 C OH
Br CH3
CH3

2-metil-2-propanol 3-bromo-3-metilciclohexanol

=>
Chapter 10 6
Alcoholes insaturados
• Grupo –OH toma precedencia.
• Use el nombre del alqueno o alquino.

OH
CH2 CHCH2CHCH3

4-penten-2-ol
=>

Chapter 10 7
Nombres comunes

CH3 OH
CH3 CH CH2OH CH3 CH CH2CH3

isobutil alcohol sec-butil alcohol

=>

Chapter 10 8
 Dioles

HO OH

hexano-1,6- diol

=>
Chapter 10 9
 Glicoles
• 1, 2 dioles (dioles vecinales) se llaman
glicoles.
glicoles

CH2CH2 CH2CH2CH3
OH OH OH OH

etano-1,2- diol propano-1,2- diol

etilen glycol propylen
p py g
glycol
y
Chapter 10
=> 10
 Fenoles

OH
OH

Cl
C H3C

3-clorofenol 4-metilfenol

=>

Chapter 10 11
 Propiedades Físicas
• Normalmente tienen altos P.Eb. Por los
P
Puentes
t ded H
H.

• Alcoholes pequeños son solubles en

agua,pero la solubilidad disminuye al
aumentar el tamaño del grupo alquílico.

=>

Chapter 10 12
Puntos de Ebullición

=>
>
Chapter 10 13
Solubilidad en Agua
g

Solubilidad disminuye
y al aumentar
tamaño del grupo alquílico.

=>
Chapter 10 14
 Metanol
• “Alcohol
Alcohol de madera”
madera
• Industrialmente se obtiene del gas natural
• Industrialmente se usa como solvente

Etanol
ƒFermentación de azucar y almidón en granos
ƒ Bebidas

Chapter 10 15
 2-Propanol
“Rubbing alcohol”

100-300 atm, 300°C

CH2 CH CH2 + H2O CH3 CH CH3
catalyst
OH

=>
Chapter 10 16
 Acidez de Alcoholes

• pKa : 15.5-18.0
15 5-18 0 (H2O: 15
15.7)
7)
• La Acidez disminuye a medida que
aumentat ell grupo alquílico.
l íli
• Los Halógenos aumentan la acidez.
• Fenol es 100 milliones de veces más
ácido que ciclohexanol!

=>
Chapter 10 17
 Formación de Iones
Alcóxidos

1
CH3CH2OH + Na CH3CH2O Na + /2 H2

Alcoholes menos reactivos se tratan con K

(más reactivo).
(CH3)3C OH + K (CH3)3CO K + 1/2 H2

=>
Chapter 10 18
 Formación de Ion
Fenóxido

O H O
+ OH
+ HOH
pKa = 15.7
pKa = 10.0

=>

Chapter 10 19
 Síntesis
• Substitución Nucleofílica de Haluros de
Alquilo.

• Hidratación de Alquenos
¾H2O en medio ácido
¾hidroboración

=>
Chapter 10 20
 Organometallic
Reagents
• Carbon is bonded to a metal (Mg or Li).
• Carbon is nucleophilic (partially
negative).
negative)
• It will attack a partially positive carbon.
¾C - X
¾C = O
• A new carbon-carbon bond forms.
=>
Chapter 10 21
 Grignard Reagents
• Formula R-Mg-X (reacts like R:- +MgX)
• Stabilized by anhydrous ether
• Iodides most reactive
• M b
May be fformed
d ffrom any halide
h lid
¾primary
¾secondary
¾tertiaryy
¾vinyl
¾aryl =>
Chapter 10 22
 Some Grignard
Reagents
Br
ether MgBr
+ Mg

Cl MgCl
ether
CH3CHCH2CH3 + Mg CH3CHCH2CH3

CH3C CH2
ether
Br + Mg CH3C CH2 =>
MgBr

Chapter 10 23
Organolithium Reagents
• Formula R-Li (reacts like R:- +Li)
• Can be produced from alkyl, vinyl, or
aryl halides
halides, just like Grignard reagents
reagents.
• Ether not necessary, wide variety of
solvents
l t can beb used. d

=>
Chapter 10 24
 Reaction with Carbonyl
• R:- attacks the partially positive carbon in the
carbonyl.
b l
• The intermediate is an alkoxide ion.
• Addition of water or dilute acid protonates the
alkoxide to p
produce an alcohol.

R
C O R C O R C OH
HOH
OH
=>
Chapter 10 25
 Synthesis of 1° Alcohols
Grignard + formaldehyde yields a primary
alcohol with one additional carbon.
CH3 H H CH3 H
H3C C CH2 C MgBr C O CH3 CH CH2 CH2 C O MgBr
H
H H H

CH3 H
HOH
CH3 CH CH2 CH2 C O H
H

=>
>
Chapter 10 26
 Synthesis of 2º Alcohols
Grignard + aldehyde yields a secondary
alcohol.
alcohol
CH3 H H3C CH3 CH3
H3C C CH2 C MgBr C O CH3 CH CH2 CH2 C O MgBr
H
H H H

CH3 CH3
HOH
CH3 CH CH2 CH2 C O H
H

=>
>
Chapter 10 27
 Synthesis of 3º Alcohols
Grignard + ketone yields a tertiary alcohol.
CH3 H H3C CH3 CH3
H3C C CH2 C MgBr C O CH3 CH CH2 CH2 C O MgBr
H3C
H H CH3

CH3 CH3
HOH
CH3 CH CH2 CH2 C O H
CH3

=>
Chapter 10 28
 How would you
synthesize…
OH CH2OH
CH3CH2CHCH2CH2CH3

OH OH
C CH3
CH3 =>
CH2CH3

Chapter 10 29
 Grignard Reactions with
Acid Chlorides and Esters
• Use two moles of Grignard reagent.
• The product is a tertiary alcohol with
y groups.
two identical alkyl g p
• Reaction with one mole of Grignard
reagent produces a ketone
intermediate, which reacts with the
second mole of Grignard reagent
reagent.
=>

Chapter 10 30
 Grignard
g + Acid
Chloride (1)
• Grignard attacks the carbonyl.
• Chloride ion leaves.
H3C CH3
R MgBr C O R C O MgBr
Cl
Cl
CH3 CH3
R C O MgBr R C + MgBrCl
O
Cl
Ketone intermediate =>

Chapter 10 31
 Grignard and Ester (1)
• Grignard attacks the carbonyl.
• Alkoxide ion leaves
H3C CH3
R MgBr C O R C O MgBr
CH3O
OCH3

CH3 CH3
R C O M B
MgBr R C + MgBrOCH3
O
OCH3
Ketone intermediate =>
Chapter 10 32
Second step of reaction
• Second mole of Grignard reacts with the
ketone intermediate to form an alkoxide ion.
• Alkoxide ion is protonated with dilute acid.
CH3 CH3
R MgBr + R C R C O MgBr
O
R

HOH
CH3
R C OH
R =>
Chapter 10 33
 How would you
synthesize...
Using an acid chloride or ester.

OH
CH3
CH3CH2CCH3 C
CH3 OH

OH
CH3CH2CHCH2CH3 =>

Chapter 10 34
 Limitations of Grignard
• No water or other acidic protons like
OH N
O-H, N-H,
H SS-H,
H or -C—C-H.
C CH G Grignard
i d
reagent is destroyed, becomes an
alkane.
lk
• No other electrophilic
p multiple
p bonds,
like C=N, C≡N, S=O, or N=O.

=>

Chapter 10 35
 Reduction of Carbonyl
• Reduction of aldehyde yields 1º alcohol.
• Reduction of ketone yields 2º alcohol.
• Reagents:
¾Sodium borohydride, NaBH4
¾Lithium aluminum hydride
hydride, LiAlH4
¾Raney nickel

=>

Chapter 10 36
 Sodium Borohydride
• Hydride ion -
ion, H , attacks the carbonyl
carbon, forming an alkoxide ion.
• Then the alkoxide ion is protonated by
dilute acid.
• Only reacts with carbonyl of aldehyde or
ketone, not with carbonyls of esters or
carboxylic acids.
O H O H O H
C C + C
H H3O
H H H
=>
Chapter 10 37
 Lithium Aluminum
Hydride
• Stronger reducing agent than sodium
borohydride, but dangerous to work with.
• Converts esters and acids to 1º
1 alcohols.
alcohols
O H O H
C C
OCH3 LAH H3O+
H =>

Chapter 10 38
 Comparison of
Reducing Agents
• LiAlH4 is stronger.
stronger
• LiAlH4 reduces more
stable compounds
which are resistant
to reduction
reduction.
=>

Chapter 10 39
Catalytic Hydrogenation
• Add H2 with Raney nickel catalyst.
• Also reduces any C=C bonds.
OH O OH

NaBH4 H2, Raney Ni

=>
Chapter 10 40
 Thiols (Mercaptans)
• Sulfur analogues of alcohols, -SH.
• Named by adding -thiol to alkane name.
• The -SH
SH group is called mercapto.
mercapto
• Complex with heavy metals: Hg, As, Au.
• More acidic than alcohols, react with
NaOH to form thiolate ion
ion.
• Stinks! =>
Chapter 10 41
 Thiol Synthesis
Use a large excess of sodium
hydrosulfide with unhindered alkyl
halide to p
prevent dialkylation
y to R-S-R.

_ _
H S R X R SH + X

=>
Chapter 10 42
 Thiol Oxidation
• Easily oxidized to disulfides, an
important feature of protein structure.
Br2
R SH + HS R R S S R + 2 HBr
Zn, HCl

•Vigorous oxidation with KMnO4,

HNO3, or NaOCl produces sulfonic acids.
O
HNO3
SH S OH
boil
O =>
>
Chapter 10 43
End of Chapter

Chapter 10 44