PROCESO OXO

(HIDROFORMILACIÓN)

ANDREA DÁVILA ALVAREZ.

INTRODUCCIÓN
HISTORIA
 DESCUBIERTA POR OTTO ROELEN EN 1938.

 LOS CATALIZADORES DE Co DOMINABAN

COMPLETAMENTE EL MERCADO HASTA
PRINCIPIOS DE 1970.

 EN EL AÑO 2004 APROXIMADAMENTE EL 75% DE

ESTE PROCESO ESTA BASADO EN CATALIZADORES
DE RODIO.
 IMPORTANCIA
 PRODUCE 15 BILLONES DE LIBRAS DE ALDEHIDOS
POR AÑO.

 ESTOS SON HIDROGENADOS A ALCOHOLES U

OXIDADOS A ÁCIDOS CARBOXILICOS.

 ESTERIFICACION DE ALCOHOLES CON ANHIDRIDO

FTÁLICO → DIALQUIL FTALATO.

 DETERGENTES Y SÍNTESIS DE FRAGANCIAS.

 DEFINICIÓN
Aldehydes
O H O
Rh or Co
R
R + CO + H
2 H
+
* R

linear (normal) branched (iso)

side reactions

R R

alkene isomerization alkene hydrogenation

 CATALIZADOR : HCO(CO)4
H
C O
O O C Co
C
O
H R C - CO
O + alkene

O O R
O O R H
C C C H CO C O
Co Co
O C Co Co C O H CO C
O
C C
C C
C O Monometallic O anti-Markovnikov
O O hydride addition
O to C=C bond to give
+ H2 Rate
linear alkyl
- CO
Determining + CO
Step
H
C O O R
O C Co R
C + CO
O O O
C C C
O C Co O C Co
O C C
O O
Bimetallic C C
proposed bimetallic O O
pathway - NOT important
in normal catalysis
increasing the CO pressure keeps the back reactions from occuring -
3 atm CO = 1.6:1 L:B ratio this limits alkene isomerization and the corresponding opportunity for
90 atm CO = 4.4:1 L:B ratio making branched alkyl
ESTUDIO CINÉTICO : HCO(CO)4
 HCO(CO)3 + CO HCO(CO)4
H
CO
Co alkene isomerization
CO
R C
O

H
OC CO CO OC CO
Co Co Co
CO CO CO
C
O R
R
linear alkyl
+CO
(leads to linear aldehyde)

O R

CO
OC Co branched acyl (leads to branched aldehyde)
CO
C
O
 22% 6% 22% 12%

65% 7% 55% 11%

% formyl group addition to indicated carbon

4% 0% 2% 1% 0.2% 12%

72% 0.6% 6% 18% 5% 38%

0.5% 15% 25%

% formyl group addition to indicated carbon

 O - H 2O O
2
R R
H H
condensation
R

O OH O
2
R R
H H
aldol
R

R
O O
R
3
R O
H
trimerization O

- H2O
2 R R
OH OH
Guerbet
R
 CATALIZADOR: HCO(CO)3(PR3)
CO CO
+ CO O
OC Co OC Co

C PR3 C PR3
O R O
R
100-180°C
+ CO 50-100 atm
- CO
5-10 times slower
+ H2
R than HCo(CO)4
Hydroformylation
H H
O
O C Co H
OC Co
C PR3 - CO C PR3
O + alkene O
R

CO O
8:1 linear:branched
R' OH OC Co H R H

C PR3
alcohol O aldehyde

R'
H
O
H R'
H
OC Co H
OC Co O
Hydrogenation C PR3
C PR3 O
O

- CO R' + CO
CO
+ H2
OC Co O

C PR3
O
 CATALIZADOR RH/PPH3
H R H
- CO + alkene
PPh3 OC PPh3 PPh3
OC Rh Rh Rh
PPh3 Ph3P H PPh3
C + CO C
O O
O

H R
H
H PPh3 OC PPh3
Rh Rh
Ph3P Ph3P
C
R R
O
O
+ CO

+ H2
O R R
- CO
PPh3 OC PPh3 PPh3
OC Rh Rh OC Rh
PPh3 Ph3P PPh3
C + CO R C
O O O
 +CO +CO +CO CO
PPh3 PPh3 CO
-PPh3 -PPh3 -PPh3
Ph3P Rh H OC Rh H OC Rh H OC Rh H
+PPh3 +PPh3 +PPh3
PPh3 PPh3 PPh3 CO
-CO -CO -CO
active, but not highly active,
Inactive Selective Catalyst not selective
very selective

Ph Ph
Ph
Ph
+ H2 P
P
Rh Rh
- benzene P
Rh Rh

Ph Ph
HIDROFORMILACIÓN RH FASE ACUOSA

TPPTS SO3 Na

P
Na O3S

Na O3S
 PRODUCTO 2 –ETIL-1-HEXANOL

 5 BILLONES DE LIBRAS POR

AÑO.

2-ethyl-hexanol
O OH O O H2
(2EH)
-H2O
2 Et Et Et Et
H H H OH
aldol Et Et Et
condensation
 NUEVA GENERACIÓN DE
CATALIZADORES RH

PPh2 PPh2 PPh2

PPh2 PPh2 PPh2

Bisbi Bisbi* Naphos

O O
O P P O
O O
O
PPh2 PPh2

UC-44 Xantphos
 Catalyst (1 Init TOF Aldehyde % iso
mM) (min-1)
1 L:B
3(1) 9:1 < 0.5
(1:400)
25(2) 70:1 < 0.5
Rh/Bisbi (1:5)

27(1) 120:1 1.5

Rh/Naphos
(1:5)
13(2) 80:1 5.0
Rh/Xantphos
(1:5)
 HIDROFORMILACIÓN
BIMETÁLICA
P PEt2 P
Ph
P Ph P Ph
Ph PEt2
Et2P Et2P

racemic-et,ph-P4 meso-et,ph-P4

Catalyst (1 mM) Init TOF (min-1) Aldehido L:B % iso

[rac-Rh2P4]2+ 20(1) 25:1 2.5

[rac-Rh2P4]2+ (30% H2O) 30(1) 33:1 < 0.5

Rh/PPh3 (1:400) 13(1) 9:1 < 0.5

Rh/Bisbi (1:5) 25(2) 70:1 < 0.5

Rh/Naphos (1:5) 27(1) 120:1 1.5

Rh/Xantphos (1:5) 13(2) 80:1 5.0

 2+

Rh Rh Ph Rh

R2P PR2 R2P P P PR2

Ph

2+

Rh Ph Rh
R2 P P P PR2

Ph
 C a ta ly s t P r e c u r s o r

1794 E t2 P P E t2
2 :1 L :B
3 5 T O /h r R h R h
1895 P P
1970
P h
P h
1929

2076 E t2 P P E t2 2+
2 5 :1 L :B R h R h
1832
1 2 0 0 T O /h r P P
P h
2096 P h
2038

2100 2000 1900 1800

W a v e n u m b e rs (c m -1)

H H 2+
O
C PEt2
CATALIZADOR Rh Rh
DIRODIO Et2P C
O
Ph P P
Ph
 O O
C 2+ + H2 C 2+
OC  CO OC
Rh Rh
Et2P CO Ph PEt2 Et2P PEt2
Ph
CO
P P P P CO
Ph Rh Ph Rh
CO H
C H
3 O A

+ CO  CO

O O O
C C 2+
2+ + H2 C H
O
C PEt2  CO H PEt2
Rh Rh Rh Rh
Et2P C Et2P C
O O
Ph P P Ph P P
Ph Ph

4 O 2*
+ 2CO
R H

R O
H 2+ H H 2+
O O
C C PEt2
PEt2 Rh Rh
Rh Rh
Et2P C Et2P C
O O
Ph P P Ph P P
Ph Ph
D
2
R

H 2+ R 2+
H H
O O
OC C PEt2 + CO C PEt2
Rh Rh Rh Rh
Et2P C Et2P C
O O
Ph P P Ph P P
Ph Ph
C B