Académique Documents
Professionnel Documents
Culture Documents
H3C
H3C-H2C-H2C
CH3
H3C
C OH
MgX
CH3-CH2-CH2MgX
CH3MgX
CH2-CH2-CH3
H3C-H2C-H2C
Johanna Raga
Alcoholes
O
2015
R1
..
R1
MgX
..
..
Cl
..
..
Cl..
..
..
O
..
..
..
Cl
R1
R MgX
Ataque a un ster
..
O
..
R1
MgX
..
O
.. R2
..
R-O..
R MgX
Johanna Raga
Alcoholes
2015
..
..
R2 O
..
..
R1
R1
R1
.. O
..
MgX
H3O+
..
..
..
R1
R1
R
..
OH
..
Alcohol terciario
R MgX
Johanna Raga
Alcoholes
2015
Hidrogenacin cataltica
O
RCH
H2
Pd, Pt, Ni o Ru
RCH2OH
Alcohol primario
O
RCR
H2
Pd, Pt, Ni o Ru
RCHR
OH
Alcohol secundario
Johanna Raga
Alcoholes
2015
H
Na+ H-B-H
H
Li+
H
H-Al-H
H
Borohidruro de sodio
(NaBH4)
Solucin acuosa
o alcohlica
Johanna Raga
Alcoholes
2015
R1
..
ter
..
C O
..
..
..
R1
R
H:-
R1
C
..
.. O
..
..
H--O--H
..
R1
H
C OH
R
Johanna Raga
Alcoholes
2015
Aldehdo
NaBH4
Cetona
LiAlH4
ster
cido carboxlico
Facilidad de
reduccin
Johanna Raga
Alcoholes
2015
Johanna Raga
Alcoholes
2015
Tosilacin
Johanna Raga
Alcoholes
2015
R-C-OH
H
[O]
O
R-C-OH
=
[O]
O
R-C-H
=
cido carboxlico
Aldehdo
Alcohol 1o
H
[O]
R-C-OH
R
O
R-C-R
Cetona
Alcohol 2o
Estructura
del ROH
R
R-C-OH
R
Johanna Raga
Alcoholes
2015
Alcohol 3o
[O]
No hay oxidacin
10
ROH primario
+
N-H CrO3Cl-
PCC en CH2Cl2
cidos
Carboxlicos
ROH primario
Aldehdos
PDC en CH2Cl2
Estructura
del ROH
ROH secundario
Agente
oxidante
Cetonas
Johanna Raga
Alcoholes
2015
11
ALCOHOLES PRIMARIOS
OH-
CO2-
CH
H+
250C
Johanna Raga
MnO2
O
COH
O
CH3-CH2-CH
=
CH3-CH2-CH2OH + PCC
CH2Cl2
CH2OH + MnO-4
O
CH3-CH2-C-OH
O
CH3-CH2-CH
CH3-CH2-CH2OH + H2CrO4
H+
Alcoholes
2015
12
ALCOHOLES SECUNDARIOS
O
CH3-(CH2)5-C-CH3
O
CH3-CH2-C-OH
=
H+
OH
CH3-(CH2)5-CH-CH3 + H2CrO4
ALCOHOLES TERCIARIOS
No hay Rx
R3COH
Productos de oxidacin
de alquenos
C C
Johanna Raga
Alcoholes
2015
13
Johanna Raga
Alcoholes
2015
14
CH3
CH3
CH3-CH-CHO
CH3-CH2-C =O
b) 2-hexanol
Johanna Raga
Alcoholes
c) Hexanal
2015
15
Johanna Raga
Alcoholes
2015
16
OH
H-X
Alcohol
R X
H-O-H
Haluro de
alquilo
ROH
(1
2 )
+ HCl
Johanna Raga
ZnCl2
R-Cl +
Alcoholes
2015
H2O
17
CH3
CH3-C-OH
CH3
HX
CH3-CH2-CH2-CH2-OH +
CH3
CH3-C-CH-CH3
H OH
CH3
CH3-C-X
CH3
CH3-CH2-CH2-CH2-X
HX
H2O
H2O
Rearreglo
CH3
CH3-C-CH-CH3
X H
HX
Johanna Raga
Alcoholes
2015
H2O
18
HClconc y ZnCl2
Tipo de alcohol
Primario
>6
Secundario
1-5
Terciario
<1
Johanna Raga
Alcoholes
2015
19
Reactivo de Lugol
(I2/KI)+NaOH
NaOI
H
R-C-CH3
OH
H
+
CH3-C-OH
O
R-C-ONa
NaOI
+ CHI3
amarillo
H
+
CH3-C-OH
O
R-C-ONa
NaOI
+ CHI3
CH3
CH3-CH2-CH2-OH +
amarillo
NaOI
NO RX
Johanna Raga
Alcoholes
2015
20
2-pentanol
3- pentanol
2-propanol
2-metil-2-propanol
Johanna Raga
Alcoholes
2015
21
3 R-OH + PCl3
3 R-Cl + P(OH)3
3 R-OH + PBr3
3 R-Br + P(OH)3
R-OH + PCl5
6 R-OH + 2 P +
3I2
2P +
6 R-I + 2 P(OH)3
3I2
2 PI3
Alcoholes
2015
22
Br
Br
..
Br
.. Br
..
..
..
..
P Br
..
R O
..
..
R-O
H
Br
Br
..
R O
H
Br-R
Br
Johanna Raga
..
O
..
..
..
.. Br
..
Alcoholes
2015
Br
P
Br
23
O
R-OH + Cl-S-Cl
Alcoholes
2015
24
..
R-O
H
..
R O
..
Cl
.. S O
..
H Cl
..
R O
Cl
..
R O
..
S
Cl
S
Cl
+ HCl
Cl-
-O
O
R
..
..
Cl
R-Cl
SO2
Cl
Cl
ster clorosulfito
R+
Johanna Raga
Alcoholes
2015
25
ROH
Primario
Secundario
Cloruro
SOCl2
SOCl2
Bromuro
PBr3
PBr3
Yoduro
P/I2
P/I2
Terciario
HCl
HBr
HI
Johanna Raga
Alcoholes
2015
26
ROH
Alcohol
H+
O
CH3-C-O-CH-CH2-CH3
=
O
CH3-C-OH
=
+ H2O
ster Orgnico
Ac. carboxlico
Reaccin reversible
CH3-CH-CH2-CH3
OH
H+
O
RCOR
=
O
RCOH
H2O
CH3
Johanna Raga
Alcoholes
2015
27
O+ H
CH3
CH3-C ..
O-H
..
CH3
+
CH3-C ..
O-H
..
H O
H
O
H
CH3
CH3
CH3-C O
H
O-H
..
..
CH3-C ..
O-H
..
O-H
..
O H
Etapa 3. Prdida de un protn del ion oxonio, formacin del intermediario tetradrico
CH3
..
..
CH3-C O
H
O-H
..
O-H
..
CH3-C O-CH
.. 3 +
O-H
..
CH3
..
..
O-H
H
Johanna Raga
Alcoholes
2015
CH3
H O
H
28
..
O-H
CH3
..
O-H
..
CH3-C O-CH
.. 3
O-H
..
CH3-C
O+
H H
H O
CH3
O
H
..
..
..
O-CH
.. 3
Etapa 5. Prdida de agua del intermediario tetradrico, formacin del ester protonado
..
..
..
O-CH
.. 3
CH3-C
CH3-C
O
+
H
H
OH
+
..
O-H
..
OCH
.. 3
CH3-C
OCH
.. 3
H
Johanna Raga
..
CH3
..
CH3
..
..
OCH
.. 3
..
CH3-C
+O
Alcoholes
2015
H O
H
29
Johanna Raga
Alcoholes
2015
30
OH
TsCl
C C
piridina
OTs
C C
Nuc:
sustitucin
C C
+ -OTs
Nuc
OTs
O eliminacin
B:
= =
O
Cl S
O
C C
C C
+ H-B
+ -OTs
CH3
Ts
p- toluensulfonilo= Tosilo
31
Cl O
.. S
R O+ O
H
O
..
R-O
.. S
O
= =
= =
R O
CH3
.. -
..
O
Cl S
O
CH3
CH3 + HCl
R-Ots
ster p-toluensulfonato
ster tosilato
SN 1
OTs Buen grupo saliente
SN 2
Ste: piridina
Johanna Raga
Alcoholes
2015
32
CH3
O
CH3CH2O S
O
= =
piridina
= =
CH3CH2OH +
O
Cl S
O
CH3
p-toluensulfonato de etilo
= =
O
CH3CH2O S
O
CH3 +
NaBr
Johanna Raga
DMSO
Alcoholes
CH3CH2-Br +
2015
NaOTs
33