CATALYSEUR PORTE ET METHODE DE FABRICATION DE MONOCARBOXYLES ANHYDRES

CARRIER-SUPPORTED CATALYST AND PROCESS FOR MAKING MONOCARBOXYLIC ANHYDRIDES

Abrégé anglais

CARRIER-SUPPORTED CATALYST AND PROCESS FOR MAKING MONO-
CARBOXYLIC ANHYDRIDES
ABSTRACT OF THE DISCLOSURE
Monocarboxylic anhydrides of the general formula (RCO)2O
are made by reacting a carboxylic acid ester or dialkylether
of the general formulae RCOOR and ROH, respectively, in which
R stands for one and the same alkyl radical having from 1 4
carbon atoms, with carbon monoxide in gas phase, in the pre-
sence of iodine or bromine or their compounds as a reaction
promoter and also in the presence of a carrier-supported
catalyst containing noble metal compounds of group VIII of
the Periodic System, at temperatures of 130 - 400°C and under
pressures of 1 - 150 bars. To this end, a novel carrier-sup-
ported catalyst is used in which the carrier material has a
noble metal/chelate-compound formed of the noble metal com-
pound and a chelator containing organonitrogen, organophos-
phorus, organoarsenic or organosulfur groups applied to it.

Revendications

23343-805
THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for making monocarboxylic anhydrides of the
general formula (RCO)2O by reacting a carboxylic acid ester or
dialkylether of the general formulae RCOOR and ROH,
respectively, in which R stands for one and the same alkyl
radical having from 1-4 carbon atoms, with carbon monoxide in
gas phase, in the presence of iodine or bromine or their
compounds as a reaction promoter and also in the presence of a
carrier-supported catalyst containing noble metal compounds
belonging to qroup VIII of the Periodic System, at temperature
of 130-400°C and under pressures of 1-150 bars, which
comprises: using a carrier-supported catalyst in which the
carrier material has a noble metal/chelate-compound formed of
the noble metal compound and a chelator containing
organonitrogen, organophosphorus, organoarsenic or organosulfur
groups applied to it.
2. A process as claimed in claim 1, wherein the carrier
material of the carrier-supported catalyst has, in addition, a
non noble metal/chelate-compound formed of a non noble metal
compound selected from the 6th or 8th subgroup of the Periodic
System of the elements and a chelator containing organo-
nitrogen, organophosphorus, organoarsenic or organosulfur
groups applied to it.
3. A process as claimed in claim 1, wherein the carrier-
supported catalyst contains a non noble metal compound
-20-

selected from the 1st through 3rd principal groups or
the 4th through 6th or 8th subgroups of the Periodic
System of the elements as an additional promoter.
4. A process as claimed in claim 1, wherein the carrier
material in the carrier-supported catalyst has a chelate
compound formed of a metal compound and one of the
following chelators
a) Y-(CH2)n-Y
b) Y-CH=CH-Y
c) 02P-CH=CH=P02
d) 02As-CH=CH-As02
e) 02P-CH2-CH2-P0-CH2-CH2-P0-CH2-CH2-P02
f) 02P-CH2-CH2-P0-CH2-CH2-P02
g) <IMG>
h) P(-CH2CH2-P02)3
i) R1-C??(CH2)n-Y-73
j) <IMG>
21

23343-806
k)
<IMG>
in which
? stands for C6H5- ;
Y stands for -NR?, an aryl group containing nitrogen,
-Pr?2, -AsR?, -SR2 or -SH ;
R1 stands for -H, a C1-C5-alkyl or -C6H5 ;
R2 stands for a C1-C6-alkyl, a C5-C8-cycloalkyl or -C6H5
or C6H5CH2- ;
n stands for 1 through 6
m stands for 0 through 8, and
x stands for 1 or 2
applied to it.
5. A process as claimed in claim 4, wherein
R2 stands for a C1-C6 alkyl, a C5-C8-cycloalkyl or -C6H5
or C6H5CH2-substituted with halogen, methoxy,
ethoxy or a C1-C3-alkyl.
6. A process as claimed in claim 1, wherein the carrier-
supported catalyst contains an inorganic oxidic carrier
or an active carbon carrier.
7. A process as claimed in claim 1, wherein the carrier-
supported catalyst contains 0.01 - 50 wgt % chelate com-
pound.
8. A process as claimed in claim 3,wherein the carrier-
supported catalyst contains altogether 0.01 - 50 wgt %
chelate compound and non noble metal compound.
9. A process as claimed in claim 1, wherein the carrier-
supported catalyst is used in the form of particles having
22

23343-806
a size of 1 through 20 mm.
10. A carrier-supported catalyst for making
monocarboxylic anhydrides by subjecting a suitable ester or
ether to a carbonylation reaction, in which the carrier has a
noble metal/chelate-compound formed of a noble metal compound
selected from the 8th subgroup of the Periodic System of the
elements and a chelator containing organonitrogen,
organophosphorus, organoarsenic or organosulfur groups applied
to it.
11. A carrier-supported catalyst as claimed in claim 10,
in which the carrier has, in addition, a non noble
metal/chelate-compound formed of a non noble metal compound
selected from the 6th or 8th subgroup of the Periodic System of
the elements and a chelator containing organonitrogen,
organophosphorus, organoarsenic or organosulfur groups applied
to it.
12. A carrier-supported catalyst as claimed in claim 10
containing a non noble metal compound selected from the 1st
through 3rd principal groups or the 4th through 6th or 8th
subgroups of the Periodic System of the elements as an
additional promoter.
13. A carrier-supported catalyst as claimed in claim 10,
in which the carrier has a chelate compound formed of a metal
compound and one of the following chelators.
-23-

a) Y-(CH2)n-Y
b) Y-CH=CH-Y
c) ?2P-CH=CH-P?2
d) ?2As-CH=CH-As?2
e) ?2p-CH2-CH2-P?-CH2-CH2-P?-CH2-CH2-P?2
f) ?2P-CH2-CH2-P?-CH2-CH2-P?2
g) <IMG>
h) P(-CH2CH2-P?2)3
i) R1-C[-(CH2)n-Y]3
j) <IMG>
k) <IMG>
24

23343-806
in which
? stands for C6H5-;
Y stands for -NR?, an aryl group containing nitrogen,
-PR?, -AsR?, -SR2 or -SH;
R1 stands for -H, a C1-C5-alkyl or -C6H5;
R2 stands for a C1-C6-alkyl, a C5-C8-cycloalkyl or
-C6H5 or C6H5CH2-;
n stands for 1 through 6, preferably 1-4;
m stands for 0 through 8, preferably 0-3, and
x stands for 1 or 2
applied to it.
14. A carrier-supported catalyst as claimed in claim 13, in
which R2 stands for a C1-C6-alkyl, a C5-C8-cycloalkyl or
-C6H5 or C6H5CH2- substituted with halogen, methoxy-,
ethoxy or a C1-C3-alkyl.
15. A carrier-supported catalyst as claimed in claim 10,
containing an inorganic oxidic carrier or active carbon
carrier.
16. A carrier supported catalyst as claimed in claim 10,
containing 0.01 - 50 wgt % chelate compound.
17. A carrier-supported catalyst as claimed in claim 12,
containing altogether 0.01 - 50 wgt % chelate compound
and non noble metal compound.
18. A carrier-supported catalyst as claimed in claim 10,
having the following formula:
carrier? [Rh((C6H5)2P-CH2CH2-P(C6H5)2)2]C1
19. A carrier-supported catalyst as claimed in claim 10,
having the following formula:
carrier? [((C6H5)2P-CH2-CH2-P(C6H5)2)2]BF4

20. A carrier-supported catalyst as claimed in claim 10,
having the following formula:
carrier? [Rh((C6H5)2P-CH2)4-P(C6H5)2)(CO)C1]2
21. A carrier-supported catalyst as claimed in claim 10,
having the following formula:
carrier ? [RH((C6H5)2PCH2CH2P(C6H5)CH2CH2P(C6H5)CH2CH2P
(C6H5)2)]PF6
22. A carrier-supported catalyst as claimed in claim 10,
having the following formula:
[Rh((C6H5)2P-CH2-CH2P(C6H5)2)2]BF4
carrier ?
[Cr(C6H5)2P-CH2-CH2-P((C6H5)2(CO)4]
23. A carrier-supported catalyst as claimed in claim 10,
having the following formula:
[Rh((C6H5)2P-CH2-CH2-P(C2H5)2)2]BF4
carrier ?
NaI
24. A carrier-supported catalyst as claimed in claim 10,
having the following formula:
carrier ? [Rh((C6H5)2P-CH=CH-P(C6H5)2)2]C104
26

Description

7 ~
HOE 85/H 007K
This invention relates to a process for making monocarboxylic
anhydrides of the general formula (RCû)20 by reacting a carboxylic
acid ester or dialkylether of the following general formulae
RCOOR and ROR, respectively, in which R stands for one and the
same alkyl group having from 1-4 carbon atoms, with carbon mon-
oxide in gas phase, in the presence of iodine or bromine or
their compounds as a reaction promoter and also in the presence
of a carrier-supported catalyst containing a noble metal com-
pound selected from group VIII of the Periodic System of the
elements, at temperatures of 130 - 400C and under pressures of
1 - 150 bars.
Processesof this kind which are carried out in gas phase
with the use of a carrier-supported catalysthave already been
described in German Specification DE~A 24 50 965 and in Japanese
Specification No, 479Zl/1975. These processes avoid the di:Efi-
culties normally accompanying operations in liquid phase, e,g.
the difficult separation and recycle of suspended and partially
dissolved catalyst and, under circumstances, promoter.
The two Specifications describe gas phase processes wherein
2n solid carrier-supported catalysts made by impregnating the
carrier material with a dissolved or suspended and even with
complex noble metal compounds are used. In this way, it is not
possible to fix e.g. an organonitrogen or organophosphorus com-
pound containing trivalent nitrogen or phosphorus in the carrier-
supported catalyst; this however has been found generally toaffect the catalyst performance and reaction selectivity.
The present invention avoids this deficiency and to this
end provides for the catalyst carrier to be impregnated with a
noble metal/chelate-compound which has one or more promoters

z~
selected from principal group V, 0.g. an organylamine or phos-
phine, al.ready integrated in it.
The invention comprises more particularly using
1) a carrier-supported ca-talyst in which the carrier has a
noble metal/chelate-compound formed of the noble metal
compound and a chelator containing organonitrogen, organo-
phosphorus, organoarsenic or organosulfur groups applied
to it.
Further preferred and optional ~eatures of the invention
1~ provide:
2) for the carrier of the carrier-supported catalyst to have
a non noble metal/chelate-compound formed of a non noble
metal compound selected from the 6th or 8th subgroup of
the Periodic System of the elements and a chelator con-
taining organonitrogen, organophosphorus, organoarsenic
or organosulfur groups additionally applied to it;
3) for the carrier-supported catalyst to contain a non noble
metal compound selected frorn the 1st through 3rd princi-
pal groups or the 4th through 6th or 8th subgroups of the
Periodic System of the elements as an additional promoter;
4) for the carrier in the carrier-supported catalyst to
have a chelate compound and one o~ the following chelators:
a) (CH2)n Y
b) Y-CH=CH-Y
.~ C) Z12P-CH-CH-P02
d) 02As-CH=CH-As02

~2~7
e ) 02P-GH2-CH2-P0-CH2-CH2-P~-CH2-CH2-P~2
f ) 02P-CH2-c~l2-P0-cH2-cH2-E02
g) , ~\y
,,I,ry
~ '
h) P( -CH2GH2-P~2) 3
i ) R1 -C/- (CH2)n-Y_73
j) ~CR1) Y
'
k) 02P- ( CH2 )x\ / ( CH2 ) x- PIZ)2
N- CH2-CH2-N
02P- (CH2 )x \ (CH2),~P02
in which
0 stands for C6H5-;
Y stands or -NR2, an aryl group containing nitrogen,
: -PR2, -AsR2, -SR2 or -SH;
Rl stands for -H, a Cl-cs-alkyl or -C6H5;
R2 stands for a Cl-C6-alkyl, a C5-C8-cycloalkyl or -C6H5
or C6H5CH2-;
n stands for i through 6, presrably 1-4;
m stands for O through 8, preferably 0-3, and

x stands for 1 or Z
applled to .it;
5) for the carrier-supported catalyst to contain an inorganic
oxidic carrier or an active carbon carrier.
6) for the carrier-supported catalyst to contain altogether
0.01 - 50 wgt %, preferably 0.1 - 20 wgt %, chelate com-
pound and non noble metal compound, if desired;
7) for the carrier-supported catalyst to be used in the form
of particles having a size of 1 through 20 mm.
The invention also relates to the catalyst itself which
is used for making monocarboxylic anhydrides by subiecting a
suitable ester or ether to a carbonylation reaction and which
is characterized in that the carrier has a noble metal/chelate-
compound formed of a noble metal belonging to the 8th subgroup
o~ the Periodic System of the elements and a chelator contain-
ing organonitrogen, organophosphorus, organoarsenic or organo-
sulfur groups applied to it.
Further preferred and optional features of the carrier-
supported catalyst of this invention provide:
1) for the carrier to have a non noble metal/chelate-compound
formed of a non noble metal selected from the 6th or 8th
subgroup of the Periodic System of the elements and a
chelator containing organonitrogen, organophosphorus,
organoarsenic or organosulfur groups additionally applied
to it;
2) for the carrier-supported catalyst to contain a non noble
metal compound selected from the 1st through 3rd principal
groups or the ~th through 6th or 8th subgroups of the
Periodic System of the elements as an additional promoter;

3) for the carrier to have a chelate compound formed of
a metal compound and one of the chelators identified
under item 4), a) through k) hereinabove applied to it;
4) Eor the carrier-supported catalyst to cDntain an in-
organic oxidic carrier or active carbon;
5) for ~he carrier-supported catalyst to cantain alto-
gether 0.01 - 50 wgt %, preferably 0.1 - 20 wgt %,
chelate compound and non noble metal compound, if
desired.
The catalyst carriers which sould preferably be used
comprise inorganic oxides, e.g. SiO2, Al203, MgO, TiO2,
La203, ZrO2, zeolite, clay, Niû, Cr2û3,-W03 or correspon-
ding mixed oxides, but also active carbon having a BET-
surface area of 1 - 1000 mZ/g, preferably 3û - 400 m2/g.
15 ~ The promoters of the 5th or 6th principal group are
chemically combined in the chelators used and constitute
themselves one of their functional groups encasing the
noble metal cumpounds selected from group VIII, especially
Rh, Ir, Pd, or Ru, and also the non noble metal compounds,
if any, selected from the 6th or 8th subgroup, especially
Cr or Ni, but also W, Fe and Co, like pincers of a cray-
fish
One of the advantages of the carrier-supported cata-
; lyst and process of this invention resides in the fact
that the promoters necessary for increasing the catalyst
performance and selectivity and selected from principal
group V or VI of the Periodic System of the elements form
a functional group Y in the chelators and thus are fixed.
It is therefore unnecessary, e.g. for an organonitrogen
or organophosphorus promoter to be separated and recycled.

The present process for making monocarboxylic anhydrides
compares favorably in its higher catalyst performance
and selectivity with the prior art methods described
hereinabove, which are also carried out in gas phase and
with the use of a carrier-supported catalyst.
A further advantage of this invention is seen to
reside in the fact that the noble metal/chelate-compounds
and optionally non noble metallchelate-compounds applied
to the carrier fail to commence melting at the reaction
temperatures necessary for making monocarboxylic anhy-
drides.
The carrier-supported catalyst and process of this
invention are more particularly used for making acetic
anhydride from methyl acetate or dimethylether in tha
presence of methyl iodide or methyl bromide as a reaction
promoter. Further suitable promoters are HI, HBr or more
ganerally RI or RBr, where R stands for an alkyl group
having 1 - 4 carbon atom~s.
The use~ul carrier materials have already been speci-
fied hereinabove; useful mixed oxides are, e.g. Cr203-
2 3' 3 1203, MgO-A1203, SiU2-A1203 or ZrO2-A1 0
The carrier-supported catalyst should preferably contain
0.01 - 5 wgt % noble metal and present a particle size
of 1 to 20 mm.
The noble metal compounds which should conveniently
be used for making the present carrier-supported catalyst,
comprise e.g. the following compounds
Rhodium:
RhC13, RhC13 . 3 H2O, RhBr3, RhI3, ~h(N03)3, Rh2(C0)4C12,

2h2(C0)4er2, Rh(C0)4I2, C P(C6H5)3 73RhCl, ~ P(C6H5)3 ~2
6( )16~ Rh4(c0)l2~ Rh2 (02CCH3)4, L RhCl(C H ) ~
Iridium:
IrCl3, L Ir(C0)3Cl ~2' Ir ~ P(C6H5)3 ]2(C ) , 4 12
~ IrCl(C8H12) ]2~ Cl(C0)zIrpyr (pyr = C6H5N);
Palladium:
PdC12, PdBr2, PdI2, (CH3cû2)2pdLp(c~Hs)3 ~2' P C 2~ ( 6 5 3 2
( 2 CH3)2, PdC12(CgHl2)~ (C6H5cN)2Pdcl2;
Ruthenium:
3' 3(C)12' RUCl2C P(~6H5)3 73, RUC12~C0)2[ P(C H )
RUcl2(co)3 J2-
Useful non noble metal compounds selected from the
6th or 3th subgroup, especially Cr, Ni, but also W, Fe, Co
which also undergo reaction with the chelator, comprise e.g.
the following:
Chromium:
Cr(C0)6, CrC13, C7H8Cr(CO)3.
Nickel:
4 ~ 5)3 ~2Ni(C0)2, NiC12, Ni(C8H12)2
The non noble metal compounds selected from the lst
through 3rd principal groups or the 4th through 6th sub-
groups or 8th subgroup of the Periodic System of the ele-
ments, preferably compounds of Li, Na, Mg, Ca, Al, li, Zr,
~, Cr, W, Fe, Co, Ni are comprised, e.g. of hydroxides,
carbonates, carbonyls, hydrides, halides and further salts.
It is possible for these non noble metal compounds to be
additionally applied to the catalyst carrier, e.g. in the
form of a solution by impregnating the carrier therewith.
for making the carrier-supported catalyst of this in-
vention, it is necessary first to have the chelator with

the functional groups Y, which is a commercially availableproduct or can be made by methods described in literature.
Speaking generally, the chelator is contacted with a
solution of one of the noble metal compounds of group VIII
and, if desired, one of the non noble metal compounds of
the 6th or 8th subgroups with the resultant formation, in
known fashion, of chelate compounds having ~elting points
higher than the temperature commonly employed in a car-
bonylation reaction for making monocarboxylic anhydrides.
Next, the carrier material is impregnated with the
dissolved con~entional chelate compounds to give the
finished catalyst. The solvents for the chelate compounds
comprise polar and unpolar solvents, e.g. dlchloromethane
(methylene chloride), chloroform, methanol, benzene,
toluene or xylene, in which the carrier material is~c;uspen-
ded. Details are indicated in the catalyst description
hereinafter.
The quantitative ratio of carboxyl.ic acid ester or di-
alkylether and iodine(compound) or bromine(compound) in the
reaction zone may vary within wide limits. Generally, how-
ever, 1 to 500 mols, preferably 1 to 100 mals, carboxy-
lic acid ester and/or dialkylether is used per 1 mol iodine'
(compound) or bromine(compound). The temperature selected
for the reaction zone should be high enough to always have
a gaseous reaction mixture therein, irrespective of the
conversion rate, and preferably is between 150 and 250C.
The preferred pressure is between 5 and 30 bars.
The reaction mixture should conveniently be contacted
with the solid carrier-supported catalyst over a period
of from 1 to 1000 seconds, preferably 1 to 180 seconds.

,~d~ G~3
The conversion should suitably be effected in a flow tube
arranged in upright position, packed with the carrier-
supported catalyst or in an autoclave provided with a
stirrer or in a shaking autoclave, having the carrier-
supported catalyst placed therein. While the carbonylationis generally effected under practically anhydrous condi-
tions, it is allowable for it to be carried out in the
presence of minor amounts of water as they are normally
found in commercially available starting materials, which
however should not exceed 1 mol %, based on the starting
materials. In addition, the carbonylation remains
substantially uneffected by the presence of minor amounts
of methanol in the starting materials or of hydrogen in
commercial carbon monoxide.
The reaction mixture coming from the carbonylation
zone is gaseous and contains carbon monoxide, methyl iodide,
acetic anhydride, unreacted methyl acetate or dimethylether
and, under circumstances, minor proportions of acetic
acid. The gaseous reaction mixture is cooled with conden-
sation of acetic anhydride, under circumstances, acetic
acid. Uncondensed gases, such as C0, CH3I, methyl acetate
or dimethylether are recycled to the reaction zone, ths
reacted ester or ether and C0 portions being continously
renewed. The anhydrides are easy to separate, i.e. in
uncomplicated fashion, by cooling the effluent reaction
mixture and recycling the uncondensed gas. This is a par-
ticular advantage of the process of this invention. The
carrier-supported catalyst is not contaminated; it remalns
; in the reaction zone. As a result, the entire process is
30 rendered considerably simpler.

7 ~
The following Examples illustrate the invention which
is naturally not llmited thereto:
Exa~ples
Autoclave test
A stainless steel (Hastelloy C) autoc:Lave (capacity
0.25 l) provided with a stirrer, various inlets and outlets
and a turnable basket receiving the catalyst was used. The
carboxylic acid ester or dialkylether was reacted in gas
phase with Cû-gas in the presence of the agitated solid
carrier-supported catalyst. The catalyst was placed in the
turnable catalyst basket which also permitted the gases to
~e mixed. The autoclave was charged with 2.5 ml of a
llquid mixture of 20 volume parts methyl iodide and 8û
volume parts ester or ether, and heated to the reaction
temperature. The carbonylation was started by injecting
; carbon monoxide. The C0-pressure was maintained constant
by continued injection o gas. Details are indicated in
the Examples.
Example 1
2 ml (1.86 9) methyl acetate, 0.5 ml (1.14 g)methyl
iodide and 1.60 9 catalyst No. 1 were reacted in the auto-
clave with carbon monoxide at 180C under a C0-pressure
of 2û bars. After a reaction period of 1 h, the catalyst
performance was found to be 260 9 Ac20 per 9 Rh per hour.
The yield of Ac20, based on the ester used, was 64 %
and the selectivity 95 %.
Example 2
2 ml (1.86 9) methyl acetate, 0.5 ml (1.14 9) methyl
iodide and 1.60 9 catalyst No. l-were reacted in the auto-
clave with carbon monoxide at 175C under a C0-pressure of

7~
20 bars. After a reaction period of l h, the catalyst perfor-
mance was found to be 220 9 Ac20 perg Rh per hour. The yield
of Ac20, based on Ihe es~,ar used, was 54 % and the selectivity
96 %.
Example 3
2 ml (1.86 g) methyl acetate, 0.5 ml (1.14 9) methyl iodide
and 1.77 g catalyst No. 2 were reacted in the autoclave with
carbon monoxide at 166C under a C0-pressure of 20 bars. After
a reaction period of 1 hour , the catalyst performance was
found to be 280 9 Ac20 per 9 Rh per hour. The yield of Ac20,
based on the ester used, was 64 % and the selectivity 97 %.
Example 4
2 ml (1.86 g) methyl acetate, 0.5 ml (1.14 9) methyl
iodide and 1.77 9 catalyst No. 2 were reacted in the auto-
~15 clave with carbon monoxide at 18ûC under a C0-pressure of
20 bars. AEter a reaction period of 1 hour, the catalyst
performance was found to be 380 g Ac20 per g Rh per hour.
The yield of Ac20, based on the ester used, was 86 % and the
selectivity 93 %.
Example 5
2 ml (1.86 9) methyl acetate, 0.5 ml (1.14 9) methyl
iodide and 1.78 9 catalyst No. 3 were reacted in the auto-
clave with carbon monoxide at 200C under a C0-pressure of
20 bars. After a reaction period of 1 hour, the catalyst
performance was found to be 35 9 Ac20 per 9 Rh per hour. The
yield of Ac20, based on the ester used, was 11.6 % and the
selectivity 87 %.

'7 ~ ~3
ExampLe 6
2 ml (1.86 9) methyl acetate, 0.5 ml (1.14 9) methyl
iodide and 1.70 9 catalyst Na . 4 were reacted in the auto-
clave with carbon monoxide at lB0C under a C0-pressure oF
20 bars. After a reaction period of 1 hour, the catalyst
performance was found to be 450 9 Ac20 per 9 Rh per hour.
The yield of Ac20, based on the ester used, was 24 ~O and
the selectivity 94.7 ~O.
Example 7
2 ml (1.86 9) methyl acetate, 0.5 ml (1.14 9) methyl
iodide and 4.4 9 catalyst No. 5 were reacted in the auto-
clave with carbon monoxide at 180C under a C0-pressure of
20 bars. After a reaction period of 1 hour, the catalys-t
performance was 150 9 Ac20 per 9 Rh per hour. The yield of
15 Ac20, based on the ester used, was 78 O and the selectivi-
ty 94 ~O.
Example 8
2 ml (1.86 9) methyl acetate, 0.5 ml (1.14 9) methyl
iodide and 1.7 9 catalyst No. 6 were reacted in the auto-
20 clave with carbon monoxide at 180C under a C0-pressure of
20 bars. After a reaction period of 1 hour, the catalyst
performance was found to be 190 9 Ac20 per 9 Rh per hour.
The yield of Ac20, based on the ester used, was 45 O and
the selectivity 93 ~O.
Example 9
A steel tube 20 mm wide and 450 mm long was used as a
flow tube in upright position and charged with 27.4 9 cata-
lyst No. 2 which however contained 0.4 wgt O Rh. 11 Nl C0
(Nl = liter measured at 0C under 1.01~ bar) and an evapo-
12

~Z~7~
rated mixture (13 ml liquid) of methyl acetate and methyl
iodide (molar ratio 11 : 1) were passed through the flow
tube at 172C under a pressure of 12.5 bars.
The effluent reaction mixture was cooled to onc at at-
mospheric pressure and analyzed gas-chromatographically.
The space/time-yield was found to be 71 9 Ac20 per liter
per hour. The yield of Ac20, based on the ester used, was
30 6 and the selectivity 96 ,6.
The carbonylation reaction was effected over a period
of 100 hours under these reaction conditions; the perfor-
mance of the carrier-supported catalyst could not be found
to have been reduced.
Example 10
2 ml (1.86 9) methyl acetate, 0.5 ml (1.14 g) methyl
iodide and l.i 9 catalyst No. 7 were reacted in the auto-
clave with carbon monoxide at 180nC under a C0-pressul~e of
2û bars. After a reaction period of 1 hour, the catalyst
performance was found to be 300 9 Ac20 per 9 Rh~hour. The
yield of Ac20, based on the ester used, was 62 6 and the
selectivity 95 6.
Example 11
1.86 9 dimethylether, 0.5 mi (1.14 9~ methyl iodide
and 1.7 9 catalyst No. 7 were reacted in the autoclave with
carbon monoxide at 180nC under a C0-pressure of 20 bars.
After a reaction period of 1 hour, the catalyst performance
was found to be 100 9 Ac20 per 9 Rh per hour. The yield of
Ac20, based on the ether used, was 20.6 O and the selecti-
vi~y 85 ~0.
Example 12
2 ml (1.86 9) methyl acetate, 0.5 ml (1.14 9) methyl
13
. ' .

L~
iodide and 1.7 9 catalyst No. 8 were reacted in the auto-
clavs with carbon monoxide at 180C under a C0-pressure of
20 bars. After a reaction period of 1 hour, the catalyst
performance was found to be 243 9 Ac20 per 9 Rh per hour.
The yield of Ac20, based on the ester used, was 50.1 O and
the selectivity 94 O.
Example 13
2 ml (1.86 g) methyl acetate, 0.5 ml (1.14 9) methyl
iodide and 1.7 9 catalyst No. 9 were reacted in the auto-
clave with carbon monoxide at 180C under a C0-pressure of
20 bars. After a reaction period of 1 hour, the catalyst
....
performance was found to be 250 9 Ac20 per 9 Rh per hour.
The yield of Ac20, based on the ester used, was 55.0 O and
the selectivity 95.5 O.
Description of catalyst preparation
In each particular case, the catalyst carrier was ac-
tivated by drying it over a period of 10 hours at 200C
under a pressure of about 0.133 millibar. All syntheses
were run in the presence of nitrogen with exclusion of oxy-
gen and water, and all reagents were previously dried usingmolecular sieve 4 A.
The following abbreviations are used hereinafter
0 C6H5
dpe = 02P-CH2CH2-P~; dpen = 02P-CH=CH-P02
dpb = 02p-(cH2)4 P~2
Tetraphos~ `2PCH2CH2P0CH2CH2P0cH2cH2P02
Catalyst No. 1
A12û3] r Rh(dpe)2_/+Cl-
3 9 activated aluminum oxide balls (99 O A1203) which
had a diameter of 3 mm, an inner BET-surface area of 125 m2/9
14

a pore volume of 0.9 ml/g were added to 150 mg (16 mg Rh)
compound of the formula / Rh(dpe)2_/Cl (melting point
217C; prepared from 1,2-bis-(diphenylphosphine)ethane and
dichlorotetracarbonyldirhodium, cf. A. Sacco et al., J.
Chem. Soc. (London) 7 (1964), 3274; for preparation of
/ Rh(C0)2Cl_/2 from RhC13 3H20 and C0-gas, see J.A.
McCleverty et al., Inorg. Synth. 8 (1966), page 211; for
preparation of 02PCH2CH2P~2, see W. Hewertscn et al., J.
Chem. Soc. (London), (1962), 1490) dissolved in 100 ml di-
chloromethane, under N2.
~he yellow suspension was heated to boiling while
stirring and refluxed over a period of 12 hours after which
the dichloromethane was found to have been completely deco-
lorized. Next, the dichloromethane was removed under redu-
ced pressure and the catalyst wa~s dried over a period of 8
hours at 85C under 1.13 millibars.
Yellow pellets containing 0.44 wgt 90 Rh wers obtained.
Catalyst No. 2
-
A1203 ¦ / Rh(dpe)2 ~ BF4
3 9 activated aluminum oxide balls (99 90 A1203) which
had a diameter of 3 mm, an inner BET-surface area of 125 m2/g
and a pore volume of 0.9 ml/g were added to 100 mg (10.4 mg
Rh) compound of the formula / Rh(dpe)2_/BF4 (melting point
= 270C; prepared the same way as catalyst No. 1 but with
an additional anion exchange with AgBF4 for increasing the
performance; cf. B.R. James et al., Can. J. Chem. 57, 180
(1979)) dissolved in 100 ml dichloromethane under N2. The
yellow suspension was heated to boiling while stirring, re-
fluxed over a period of 12 hours after which the dichloro-

~;7~
methane was found to have been completely decolorized.
Next, the dichloromethane was removed under reduced pressu-
re and the catalyst was dried for ~ hours at 85C under
1.13 millibars.
Yellow pellets containing 0.32 wyt q Rh were obtained.
Catalyst No. 3
5i21 / Rh(dpe)2-/ BF4
4 g activated silicon dioxide (98 O SiO2) which had a
diameter of 3 mm, an inner BET-surface area of 280 m2/g and
a pore volume of n.9s ml/g was added to 193 mg (2û.1 mg Rh)
compound of the formula / Rh(dpe)2_/BF4 dissolved in 100 ml
dichloromethane under N2. The yellow suspension was heated
to boiling while stirring and refluxed over a period of 12
hours after which the dichloromethane was found to have
been completely decolorized. Next, the dichlorornethane was.
removed under reduced pressure and the catalyst.was dried
for 8 hours at 85~C under 1.13 millibars.
Yellow pellet~s containing 0.47 wgt ' Rh were obtained.
Catalyst No. 4
A1203 ~ r Rh(dpb)(CO)C1 72
5.3 9 activated aluminum oxide balls (99 ~O A1203)
which had a diameter of 3 mm, an inner BET-surface area of
125 m2/g and a pore volume of 0.9 ml/g were added to 29 mg
(5.04 mg Rh) compound of the formula / Rh(dpe)(CO)Cl_72
(melting point - 182~C; prepared from 1,4-bis-(diphenylphos-
phine)butane and dichlorotetracarbonyldirhodium; cf. A.R.
Sanger, 0. Chem. Soc. Dalton Trans (1977)j 120) dissolved
in 50 ml dichloromethane, under N2. The yellow suspens~.on
was heated to boiling while stirring and refluxed over a
16

period of 1~ hours after which the dichloromethane solvent
was found to have been completely decolorized. Next, the
dichloromethane was removed under reduced pressure and the
catalyst was dried for 8 hours at 85C under 1.13 milli-
bars.
Yellow pellets containing 0.08 wgt O Rh were obtained.
Catalyst No. 5
Cr2~3
/ Rh(dpe)2_/ BF4
A1203
6.3 9 activated chromium/aluminum oxide cylinders
(5.29 9 A1203 + 1.01 9 Cr203) with the dimensions of 4 x 4
mm and with an inner BET-surface area of 68 m2/g were added
to 200 mg (20.9 mg Rh) compound of the formula ~ Rh(dpe)2_78F4
dissolved in 100 ml dichloromethane, under Nz. The green
suspension was heated to boiling while stirring and reflu-
xed over a period of 24 hours after which the dichlorome-
thane was found to have been completely decolorized. Next,
the dichloromethane was removed under reduced pressure and
the catalys-t was dried for 8 hours at 85C under 1.13 mil-
libars. Green pellets containing 0.3 wgt ~O Rh were obtain-
ed.
Catalyst No. 6
A1203 ] / Rh(tetraphos I)_/ PF6
3.5 9 activated aluminum oxide balls (99 O A1203)
which had a diameter of 3 mm, an inner BFT-surface area of
125 m2/g and a pore volume of û.9 ml/g were added to 100 ml
(11 mg Rh) compound of the formula ~ Rh(tetraphos-I)_/+PF6
(melting point = 314C; prepared from (P03)3RhCl and tetra-
phos-I; cf. R.B. King et al., Inorg. Chem. Vol. 10 (1971),
17

7~
page 1851 et seq) dissolved in 50 ml dichloromethane, under
N2. The yellow suspension was heated to boiling while
stirring and refluxed over a period of 16 hcurs after which
the dichloromethane was found to have been completely deco-
lorized. Next, the dichloromethane W25 removed under redu-
ced pressure and the catalyst was dried for 8 hours at 85C
under 1.13 millibars.
Yellow pellets containing 0.3 wgt ~O Rh were obtained
Catalyst No. 7
_ ~ Rh(dpe)2_/ BF4
A12U3
_ r ~r(dpe)(CQ)4_/
~ g activated aluminum oxide balls (99 ~O A1203) which
had a diameter of 3 mm, an inner BET-surface area of 125
m2/g and a pore volume of 0.9 ml/g were added to 100 mg
(10.4 rng Rh) compound of the formula ~ Rh(dpe)2_7BF4 and
100 mg (9.25 mg Cr) compound of the Formula ~ Cr(dpe)(C0)4 7
(prepared as described by J. Chatt et al., J. Chem. Soc.
(London) 1961, pages 4980 et seq.) dissolved in 100 ml di-
chloromethane, under N2. The yellow suspension was heated
to boiling while stirring and refluxed over a period of 12
hours after which the dichloromethane was found to have
been completely decolorized. Next, the dichloromethane was
rernoved under reduced pressure and the catalyst was dried
for 8 hours at 85C under 1.13 millibars. Yellow pellets
containing 0.31 wgt O Rh and 0.28 wgt O Cr were obtained.
Catalyst No. 8
/ Rh(dpe)2_/~BFe4
A123
NaI
18

~;'7~
0.1 y sodium iodide dissolved in 30 ml acetone wasadded while stirring to 3 9 activated aluminum oxide balls
(99 6 A1203) which had a diameter of 3 mm, an inner BET
surface area of 125 m2/g and a pore volume of 0.9 ml/g, and
the whole was heated to boiling, and refluxed over a period
of ~8 hours. Next, the solvent was removed and the catalyst
balls were dried for 8 hours at 85~C under 1.13 millibars.
The rhodium was applied as described hereinabove For
catalyst No. 2
Yellow pellets containing û.31 wgt O Rh and 3.12 wgt 6
NaI were obtained.
Catalyst No. 9
123 ] / Rh(dpen~2_ 7 C104e
10Q mg (10.3 mg Rh) compound of the formula / Rh(dpen)
C104 (prepared as described by W.A. Fordyce et al., Inorg.
Chem. 1982, 2i, pages 1455-61) dissolved in 100 ml dichlo-
romethane was added under N2 to 3 g activated a1uminum oxi-
de balls (99 6 A1203) which had a diameter of 3 mm, an in-
ner BET-surface area oF 125 m2/g and a pore volume of 0.9
ml/g. The light yellow suspension was heated to boiling and
reflu~ed over a period of 12 hours after which the solvent
was found to have been completely decolorized. Next, the
solvent was removed under reduced pressure and the catalyst
was dried for 8 hours at 85~C under 1.13 mll1ibars. Yello-
wish pelle~s containing 0.33 wgt X Rh were obtained.
19