Title: Method for hydroformylation, xanthene-bridged ligands and catalyst comprising a complex of said ligands
Abstract: In a process for the hydroformylation of ethylenically unsaturated compounds, at least one complex of a metal of transition group VIII. with at least one phosphorus-, arsenic- or antimony-containing compound as ligand is used as hydroformylation catalyst, where the compound used as ligand in each case comprises two groups which comprise a P, As or Sb atom and at least two further hetero atoms and are bound to a xanthene-like molecular framework. New compounds of this type and catalysts which comprise at least one complex of a metal of transition group VIII. with at least one such compound as ligand are also provided.
Patent Number: 6,881,867 Issued on 04/19/2005 to Ahlers, et al.
| Inventors:
|
Ahlers; Wolfgang (Worms, DE);
Wiebelhaus; Dag (Neustadt, DE);
Paciello; Rocco (Bad Durkheim, DE);
Bartsch; Michael (Neustadt, DE);
Baumann; Robert (Mannheim, DE);
Vogt; Dieter (Eindhoven, NL);
Hewat; Alison (Eindhoven, NL)
|
| Assignee:
|
BASF Aktiengesellschaft (Ludwigshafen, DE)
|
| Appl. No.:
|
380054 |
| Filed:
|
March 11, 2003 |
| PCT Filed:
|
September 17, 2001
|
| PCT NO:
|
PCT/EP01/10735
|
| 371 Date:
|
March 11, 2003
|
| 102(e) Date:
|
March 11, 2003
|
| PCT PUB.NO.:
|
WO02/22261 |
| PCT PUB. Date:
|
March 21, 2002 |
Foreign Application Priority Data
| Sep 18, 2000[DE] | 100 46 026 |
| Current U.S. Class: |
568/451; 568/454; 502/150; 502/158; 502/162; 502/168; 544/89; 544/338; 546/26; 549/16 |
| Intern'l Class: |
C07C 045//50; B01J 031//00; C07D 265//12; C07D 221//18; C07D 327//06 |
| Field of Search: |
568/451,454
502/150,158,162,168
544/89,338
546/26
549/16
|
References Cited [Referenced By]
U.S. Patent Documents
| 6265620 | Jul., 2001 | Urata et al. | 568/454.
|
| 6342605 | Jan., 2002 | Geissler et al. | 546/22.
|
| 6486359 | Nov., 2002 | Maas et al. | 568/454.
|
| Foreign Patent Documents |
| 95/30680 | Nov., 1995 | WO.
| |
| 99/21013 | Apr., 1999 | WO.
| |
| 99/65606 | Dec., 1999 | WO.
| |
Other References
J.Chem.Soc.,1998 2981-2988, Goertz.
Chem.Eur.J.2001,7,No. 8, Goertz et al.
Angew.Chem.Int.Ed.1998,37,No. 22, Dierkes et al.
Organometallics 1999,18,4765-4777,van der Veen et al.
Organometallics 1995,14,3081-3089,Kranenburg et al.
Chem.Ber.124 (1991)1705-1710, Haenel et al.
Tetr.Ltrs.vol. 34,No. 13, 2017-2119, 1993, Haenel et al.
Tetr.Ltrs.vol. 36,No. 1,75-78,1995, Hillebrand et al.
Angew.Chem.2000,112,Nr.9, Selent et al., 1694-1696.
Thesis "Zur selektiven nickelkatalysierten Hydrocyanierung von Olefinen"
(Concerning the selective nickel catalyzed hydrocyanation of olefins)
1998.
|
Primary Examiner: Richter; Johann
Assistant Examiner: Witherspoon; Sikarl A.
Attorney, Agent or Firm: Keil & Weinkauf
Claims
We claim:
1. A process for the hydroformylation of compounds containing at least one
ethylenically unsaturated double bond by reaction with carbon monoxide and
hydrogen in the presence of a hydroformylation catalyst comprising at
least one complex of a metal of transition group VIII with at least one
ligand selected from among compounds of the general formula I
##STR14##
where
A.sup.1 and A.sup.2 are each, independently of one another, O, S, SiR.sup.a
R.sup.b, NR.sup.c or CR.sup.5 R.sup.6, where
R.sup.a, R.sup.b, R.sup.c, R.sup.5 and R.sup.6 are each, independently of
one another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or
hetaryl,
Y.sup.1 and Y.sup.2 are each, independently of one another, radicals
containing at least one phosphorus, arsenic or antimony atom, where in
each case at least two substituted or unsubstituted heteroatoms selected
from among O, S and NR.sup.c, where R.sup.c is hydrogen, alkyl, cycloalkyl
or aryl, are directly bound to the phosphorus, arsenic or antimony atom,
and
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each, independently of one
another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl,
COOR.sup.d, COO.sup.- M.sup.+, SO.sub.3 R.sup.d, SO.sup.-.sub.3 M.sup.+,
NE.sup.1 E.sup.2, NE.sup.1 E.sup.2 E.sup.3+ X.sup.-, alkylene-NE.sup.1
E.sup.2 E.sup.3+ X.sup.-, OR.sup.d, SR.sup.d, (CHR.sup.e CH.sub.2 O).sub.x
R.sup.d, (CH.sub.2 N(E.sup.1)).sub.x R.sup.d, (CH.sub.2 CH.sub.2
N(E.sup.1)).sub.x R.sup.d, halogen, trifluoromethyl, nitro, acyl or cyano,
where
R.sup.d, E.sup.1, E.sup.2 and E.sup.3 are identical or different radicals
selected from among hydrogen, alkyl, cycloalkyl and aryl,
R.sup.e is hydrogen, methyl or ethyl,
M.sup.+ is a cation,
X.sup.- is an anion, and
x is an integer from 1 to 120, or
R.sup.1 and/or R.sup.3 together with two adjacent carbon atoms of the
benzene ring to which they are bound form a fused ring system having 1, 2
or 3 further rings.
2. A process as claimed in claim 1, wherein, in the formula I, Y.sup.1 and
Y.sup.2 are each, independently of one another, a radical of the formula
P(OR.sup.7)(OR.sup.8), OP(OR.sup.7)R.sup.8 or OP(OR.sup.7)(OR.sup.8),
where
R.sup.7 and R.sup.8 are each, independently of one another, alkyl,
cycloalkyl, heterocycloalkyl, aryl or hetaryl which may bear one, two or
three substituents selected from among alkyl, cycloalkyl,
heterocycloalkyl, aryl, hetaryl, COOR.sup.f, COO.sup.- M.sup.+, SO.sub.3
R.sup.f, SO.sup.-.sub.3 M.sup.+, NE.sup.4 E.sup.5, alkylene-NE.sup.4
E.sup.5, NE.sup.4 E.sup.5 E.sup.6+ X.sup.-, alkylene-NE.sup.4 E.sup.5
E.sup.6+ X.sup.-, OR.sup.f, SR.sup.f, (CHR.sup.g CH.sub.2 O).sub.y
R.sup.f, (CH.sub.2 N(E.sup.4)).sub.y R.sup.f, (CH.sub.2 CH.sub.2
N(E.sup.4)).sub.y R.sup.f, halogen, trifluoromethyl, nitro, acyl and
cyano,
where
R.sup.f, E.sup.4, E.sup.5 and E.sup.6 are identical or different radicals
selected from among hydrogen, alkyl, cycloalkyl or aryl,
R.sup.g is hydrogen, methyl or ethyl,
M.sup.+ is a cation,
X.sup.- is an anion, and
y is an integer from 1 to 120, or
R.sup.7 and R.sup.8 together with the phosphorus atom and the oxygen
atom(s) to which they are bound form a 5- to 8-membered heterocycle to
which one, two or three cycloalkyl, heterocycloalkyl, aryl or hetaryl
groups may additionally be fused, where the heterocycle and, if present,
the fused-on groups may each bear, independently of one another, one, two,
three or four substituents selected from among alkyl, cycloalkyl,
heterocycloalkyl, aryl, hetaryl, COOR.sup.f, COO.sup.- M.sup.+, SO.sub.3
R.sup.f, SO.sup.-.sub.3 M.sup.+, NE.sup.4 E.sup.5, alkylene-NE.sup.4
E.sup.5, NE.sup.4 E.sup.5 E.sup.6+ X.sup.-, alkylene-NE.sup.4 E.sup.5
E.sup.6+ X.sup.-, OR.sup.f, SR.sup.f, (CHR.sup.g CH.sub.2 O).sub.y
R.sup.f, (CH.sub.2 N(E.sup.4)).sub.y R.sup.f, (CH.sub.2 CH.sub.2
N(E.sup.4)).sub.y R.sup.f, halogen, trifluoromethyl, nitro, acyl and
cyano, where R.sup.f, R.sup.g, E.sup.4, E.sup.5, E.sup.6, M.sup.+, X.sup.-
and y are as defined above.
3. A process as claimed in claim 1, wherein the compound of the formula I
is selected from among compounds of the formulae I.1 to I.6
##STR15##
##STR16##
A.sup.1 is O, S or CR.sup.5 R.sup.6, where R.sup.5 and R.sup.6 are each,
independently of one another, hydrogen or C.sub.1-C.sub.4 -alkyl,
R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22, R.sup.23 and
R.sup.24 are each, independently of one another,
hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, COOR.sup.f,
COO.sup.- M.sup.+, SO.sub.3 R.sup.f, SO.sup.-.sub.3 M.sup.+, NE.sup.4
E.sup.5, alkylene-NE.sup.4 E.sup.5, NE.sup.4 E.sup.5 E.sup.6+ X.sup.-,
alkylene-NE.sup.4 E.sup.5 E.sup.6+ X.sup.-, OR.sub.f, SR.sup.f, (CHR.sup.g
CH.sub.2 O).sub.y R.sup.f, (CH.sub.2 N(E.sup.4)).sub.y R.sup.f, (CH.sub.2
CH.sub.2 N(E.sup.4)).sub.y R.sup.f, halogen, trifluoromethyl, nitro, acyl
and cyano,
where
R.sup.f, E.sup.4, E.sup.5 and E.sup.6 are identical or different radicals
selected from among hydrogen, alkyl, cycloalkyl and aryl,
R.sup.g is hydrogen, methyl or ethyl,
M.sup.+ is a cation,
X.sup.- is an anion, and
y is an integer from 1 to 120.
4. A process as claimed in claim 2, wherein the metal of transition group
VIII is selected from among cobalt, ruthenium, iridium, rhodium, palladium
and platinum.
5. A process as claimed in claim 3, wherein the catalyst further comprises
at least one additional ligand selected from among halides, amines,
carboxylates, acetylacetonate, arylsulfonates and alkylsulfonates,
hydride, CO, olefins, dienes, cycloolefins, nitriles, N-containing
heterocycles, aromatics and heteroaromatics, ethers, PF.sub.3, phospholes,
phosphabenzenes and monodentate, bidentate and polydentate phosphine,
phosphinite, phosphonite, phosphoramidite and phosphite ligands.
6. A process as claimed in claim 4, wherein the unsaturated compound used
for the hydroformylation is selected from among internal linear olefins
and olefin mixtures in which at least one internal linear olefin is
present.
Description
The present invention relates to a process for the hydroformylation of
ethylenically unsaturated compounds, in which at least one complex of a
metal of transition group VIII with at least one phosphorus-, arsenic- or
antimony-containing compound as ligand is used as hydroformylation
catalyst, where the compound used as ligand in each case comprises at
least two groups which comprise a P, As or Sb atom and at least two
further hetero atoms and are bound to a xanthene-like molecular framework.
The invention also provides new compounds of this type and catalysts which
comprise at least one complex of a metal of transition group VIII with at
least one such compound as ligand.
Hydroformylation or the oxo process is an important industrial process and
is employed for preparing aldehydes from olefins, carbon monoxide and
hydrogen. If desired, these aldehydes can be hydrogenated by means of
hydrogen in the same process step to give the corresponding oxo alcohols.
The reaction itself is strongly exothermic and generally proceeds under
superatmospheric pressure and at elevated temperatures in the presence of
catalysts. Catalysts used are Co, Rh, Ir, Ru, Pd or Pt compounds or
complexes which may be modified with N- or P-containing ligands to
influence the activity and/or selectivity. The hydroformylation reaction
results in formation of mixtures of isomeric aldehydes because of the
possible CO addition on to each of the two carbon atoms of a double bond.
In addition, double bond isomerization, i.e. shifting of internal double
bonds to a terminal position and vice versa, can also occur.
Owing to the substantially greater industrial importance of
.alpha.-aldehydes, optimization of the hydroformylation catalysts to
achieve a very high hydroformylation activity together with a very low
tendency to form double bonds not in the .alpha. position is sought. In
addition, there is a need for hydroformylation catalysts which lead to
good yields of .alpha.-aldehydes and in particular n-aldehydes even when
internal linear olefins are used as starting materials. Here, the catalyst
must make possible both the establishment of equilibrium between internal
and terminal double bond isomers and the very selective hydroformylation
of the terminal olefins.
The use of phosphorus-containing ligands for stabilizing and/or activating
the catalyst metal in rhodium-catalyzed low-pressure hydroformylation is
known. Suitable phosphorus-containing ligands are, for example,
phosphines, phosphinites, phosphonites, phosphites, phosphoramidites,
phospholes and phosphabenzenes. The most widespread ligands at present are
triarylphosphines such as triphenylphosphine and sulfonated
triphenylphosphine, since these have sufficient stability under the
reaction conditions. However, a disadvantage of these ligands is that, in
general, only very high ligand excesses give satisfactory yields, in
particular of linear aldehydes.
In Angew. Chem. Int. Ed. 39, 1639 (2000), D. Selent et al. describe the
isomerizing hydroformylation of internal olefins in the presence of
rhodium catalysts, with oxy-functionalized bisphenyl monophosphonites
being used as ligands. A disadvantage of these catalysts is their low
n-selectivity. Thus, in the hydroformylation of isomeric n-octenes,
n-nonanal is obtained in a yield of at most 47.9%.
WO-A-98/43935 describes the use of chelating ligands in catalysts for
hydroformylation.
In Tetrahedron Letters, Volume 34, No. 13, pages 2107 ff. (1993), in
Tetrahedron Letters, Volume 36, No. 1, pages 75 ff. (1995) and in Chem.
Ber. 124, page 1705 ff. (1991), Haenel et al. describe the synthesis of
bis(diphenylphosphino)chelates having anthracene, dibenzofuran,
dibenzothiophene and xanthene skeletons. The use of these compounds as
catalysts is not described.
In J. Chem. Soc., Dalton Trans., 1998, pp. 2981-2988, W. Goertz et al.
describe the use of chelating phosphines and phosphonites having a
thioxanthene skeleton for the nickel-catalyzed hydrocyanation of styrene.
Use in hydroformylation is not described.
In Organometallics 1995, 14, pages 3081 to 3089, M. Kranenburg et al.
describe chelating phosphines having a xanthene skeleton and their use for
regioselective rhodium-catalyzed hydroformylation. Chelating phosphonites
and phosphites are not described in this document. A disadvantage of these
chelating phosphines is that they are not suitable for the isomerizing
hydroformylation of internal olefins with high .alpha.- or n-selectivity.
In Organometallics 1999, 18, pages 4765 to 4777, van der Veen et al.
describe the use of phosphacyclic diphosphines having a xanthene skeleton
as ligands for rhodium-catalyzed hydroformylation. A disadvantage of these
catalysts is their very low activity which makes their use in industrial
processes uneconomical.
WO 95/30680 describes bidentate phosphine ligands in which the phosphorus
atoms may be bound to a xanthene skeleton and the use of these ligands in
catalysts for hydroformylation. A disadvantage of these catalysts is that
they are not suitable for the isomerizing hydroformylation of internal
olefins with good .alpha.- or n-selectivity.
EP-A-0982314 describes bidentate carbocyclic or heterocyclic phosphine
ligands and a process for preparing linear aldehydes by hydroformylation
of internal olefins using such ligands. A disadvantage of these ligands is
their very low activity which makes use in industrial processes
uneconomical.
DE-A-19827232 describes catalysts based on monodentate, bidentate or
polydentate phosphinite ligands in which the phosphorus atom and the
oxygen atom of the phosphinite group are part of a 5- to 8-membered
heterocycle, and their use in hydroformylation and hydrocyanation. The
bidentate ligands may have a xanthene skeleton. A disadvantage of these
ligands is that they are in need of improvement in terms of the .alpha.-
or n-selectivity in the isomerizing hydroformylation of internal olefins.
None of the abovementioned documents describes the use of chelating
phosphonites and phosphites having a xanthene skeleton as ligands in
catalysts for hydroformylation.
It is an object of the present invention to provide an improved process for
the hydroformylation of compounds containing at least one ethylenically
unsaturated double bond. Here, a very high proportion of .alpha.-aldehydes
or .alpha.-alcohols should preferably be obtained in the hydroformylation
of .alpha.-olefins. In particular, the process should be suitable for the
hydroformylation of internal linear olefins with high regioselectivity in
favor of terminal product aldehydes. A further object of the invention is
to provide new compounds and novel catalysts comprising at least one
complex of a metal of transition group VIII with such a compound as
ligand.
We have found that these objects are achieved by a hydroformylation process
in which at least one complex of a metal of transition group VIII with at
least one phosphorus-, arsenic- and/or antimony-containing compound as
ligand is used as hydroformylation catalyst. This compound comprises two
groups comprising a P, As and/or Sb atom, with the P, As and Sb atoms
being bound directly to at least two further hetero atoms and with each of
the two groups being bound to a different phenyl ring of a xanthene
skeleton. The group is bound directly to the phenyl ring via the
phosphorus, arsenic or antimony atom or via a hetero atom bound thereto.
The present invention accordingly provides a process for the
hydroformylation of compounds containing at least one ethylenically
unsaturated double bond by reaction with carbon monoxide and hydrogen in
the presence of a hydroformylation catalyst comprising at least one
complex of a metal of transition group VIII with at least one ligand
selected from among compounds of the general formula I
##STR1##
where
A.sup.1 and A.sup.2 are each, independently of one another, O, S, SiR.sup.a
R.sup.b, NR.sup.c or CR.sup.5 R.sup.6, where
R.sup.a, R.sup.b, R.sup.c, R.sup.5 and R.sup.6 are each, independently of
one another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or
hetaryl,
Y.sup.1 and Y.sup.2 are each, independently of one another, radicals
containing at least one phosphorus, arsenic or antimony atom, where in
each case at least two substituted or unsubstituted hetero atoms selected
from among O, S and NR.sup.c, where R.sup.c is hydrogen, alkyl, cycloalkyl
or aryl, are directly bound to the phosphorus, arsenic or antimony atom,
and
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each, independently of one
another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl,
COOR.sup.d, COO.sup.- M.sup.+, SO.sub.3 R.sup.d, SO.sup.-.sub.3 M.sup.+,
NE.sup.1 E.sup.2, NE.sup.1 E.sup.2 E.sup.3+ X.sup.-, alkylene-NE.sup.1
E.sup.2 E.sup.3+ X.sup.-, OR.sup.d, SR.sup.d, (CHR.sup.e CH.sub.2 O).sub.x
R.sup.d, (CH.sub.2 N(E.sup.1)).sub.x R.sup.d, (CH.sub.2 CH.sub.2
N(E.sup.1)).sub.x R.sup.d, halogen, trifluoromethyl, nitro, acyl or cyano,
where
R.sup.d, E.sup.1, E.sup.2 and E.sup.3 are identical or different radicals
selected from among hydrogen, alkyl, cycloalkyl and aryl,
R.sup.e is hydrogen, methyl or ethyl,
M.sup.+ is a cation,
X.sup.- is an anion, and
x is an integer from 1 to 120, or
R.sup.1 and/or R.sup.3 together with two adjacent carbon atoms of the
benzene ring to which they are bound form a fused ring system having 1, 2
or 3 further rings.
For the purposes of the present invention, the expression `alkyl`
encompasses straight-chain and branched alkyl groups. They are preferably
straight-chain or branched C.sub.1 -C.sub.12 -alkyl groups, more
preferably C.sub.1 -C.sub.8 -alkyl groups and particularly preferably
C.sub.1 -C.sub.4 -alkyl groups. Examples of alkyl groups are, in
particular, methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl,
tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl,
1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl,
n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,
1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl,
1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl,
1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl,
1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl,
1-propylbutyl, octyl.
Substituted alkyl radicals preferably have 1, 2, 3, 4 or 5, in particular
1, 2 or 3, substituents selected from among cycloalkyl, aryl, hetaryl,
halogen, NE.sup.1 E.sup.2, NE.sup.1 E.sup.2 E.sup.3+, carboxyl,
carboxylate, --SO.sub.3 H and sulfonate.
A cycloalkyl group is preferably a C.sub.5 -C.sub.7 -cycloalkyl group such
as cyclopentyl, cyclohexyl and cycloheptyl.
If the cycloalkyl group is substituted, it preferably has 1, 2, 3, 4 or 5,
in particular 1, 2 or 3, substituents selected from among alkyl, alkoxy
and halogen.
Aryl is preferably phenyl, tolyl, xylyl, mesityl, naphthyl, anthracenyl,
phenanthrenyl, naphthacenyl, in particular phenyl or naphthyl.
Substituted aryl radicals preferably have 1, 2, 3, 4 or 5, in particular 1,
2 or 3, substituents selected from among alkyl, alkoxy, carboxyl,
carboxylate, trifluoromethyl, --SO.sub.3 H, sulfonate, NE.sup.1 E.sup.2,
alkylene-NE.sup.1 E.sup.2, nitro, cyano and halogen.
Hetaryl is preferably pyridyl, quinolinyl, acridinyl, pyridazinyl,
pyrimidinyl or pyrazinyl.
Substituted hetaryl radicals preferably have 1, 2 or 3 substituents
selected from among alkyl, alkoxy, carboxyl, carboxylate, --SO.sub.3 H,
sulfonate, NE.sup.1 E.sup.2, alkylene-NE.sup.1 E.sup.2, trifluoromethyl
and halogen.
What has been said above in respect of alkyl, cycloalkyl and aryl radicals
applies analogously to alkoxy, cycloalkyloxy and aryloxy radicals.
The radicals NE.sup.1 E.sup.2 and NE.sup.4 E.sup.5 are preferably
N,N-dimethylamino, N,N-diethylamino, N,N-dipropylamino,
N,N-diisopropylamino, N,N-di-n-butylamino, N,N-di-t-butylamino,
N,N-dicyclohexylamino or N,N-diphenylamino.
Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine,
chlorine or bromine.
For the purposes of the present invention, carboxylate and sulfonate are
preferably each a derivative of a carboxylic acid function or a sulfonic
acid function, in particular a metal carboxylate or sulfonate, a
carboxylic ester or sulfonic ester function or a carboxamide or
sulfonamide function. These include, for example, esters of C.sub.1
-C.sub.4 -alkanoles such as methanol, ethanol, n-propanol, isopropanol,
n-butanol, sec-butanol and tert-butanol.
Y.sup.1 and Y.sup.2 are preferably each a radical containing a phosphorus
atom and in particular a radical of the formula P(OR.sup.7)(OR.sup.8),
OP(OR.sup.7)R.sup.8 or OP(OR.sup.7)(OR.sup.8), where
R.sup.7 and R.sup.8 are each, independently of one another, alkyl,
cycloalkyl, heterocycloalkyl, aryl or hetaryl which may bear one, two or
three substituents selected from among alkyl, cycloalkyl,
heterocycloalkyl, aryl, hetaryl, COOR.sup.f, COO.sup.- M.sup.+, SO.sub.3
R.sup.f, SO.sup.-.sub.3 M.sup.+, NE.sup.4 E.sup.5, alkylene-NE.sup.4
E.sup.5, NE.sup.4 E.sup.5 E.sup.6+ X.sup.-, alkylene-NE.sup.4 E.sup.5
E.sup.6+ X.sup.-, OR.sup.f, SR.sup.f, (CHR.sup.g CH.sub.2 O).sub.y
R.sup.f, (CH.sub.2 N(E.sup.4)).sub.y R.sup.f, (CH.sub.2 CH.sub.2
N(E.sup.4)).sub.y R.sup.f, halogen, trifluoromethyl, nitro, acyl and
cyano,
where
R.sup.f, E.sup.4, E.sup.5 and E.sup.6 are identical or different radicals
selected from among hydrogen, alkyl, cycloalkyl or aryl,
R.sup.g is hydrogen, methyl or ethyl,
M.sup.+ is a cation,
X.sup.- is an anion, and
y is an integer from 1 to 120, or
R.sup.7 and R.sup.8 together with the phosphorus atom and the oxygen
atom(s) to which they are bound form a 5- to 8-membered heterocycle to
which one, two or three cycloalkyl, heterocycloalkyl, aryl or hetaryl
groups may additionally be fused, where the heterocycle and, if present,
the fused-on groups may each bear, independently of one another, one, two,
three or four substituents selected from among alkyl, cycloalkyl,
heterocycloalkyl, aryl, hetaryl, COOR.sup.f, COO.sup.- M.sup.+, SO.sub.3
R.sup.f, SO.sup.-.sub.3 M.sup.+, NE.sup.4 E.sup.5, alkylene-NE.sup.4
E.sup.5, NE.sup.4 E.sup.5 E.sup.6+ X.sup.-, alkylene-NE.sup.4 E.sup.5
E.sup.6+ X.sup.-, OR.sup.f, SR.sup.f, (CHR.sup.g CH.sub.2 O).sub.y
R.sup.f, (CH.sub.2 N(E.sup.4)).sub.y R.sup.f, (CH.sub.2 CH.sub.2
N(E.sup.4)).sub.y R.sup.f, halogen, trifluoromethyl, nitro, acyl and
cyano, where R.sup.f, R.sup.g, E.sup.4, E.sup.5, E.sup.6, M.sup.+, X.sup.-
and y are as defined above.
In a preferred embodiment, one of the radicals Y.sup.1 or Y.sup.2 or both
radicals Y.sup.1 and Y.sup.2 in the formula I are selected from among
radicals of the formulae P(OR.sup.7)(OR.sup.8), OP(OR.sup.7)R.sup.8 and
OP(OR.sup.7)(OR.sup.8) in which R.sup.7 and R.sup.8 together with the
phosphorus atom and the oxygen atom(s) to which they are bound form a 5-
to 8-membered heterocycle to which one, two or three cycloalkyl,
heterocycloalkyl, aryl and/or hetaryl groups may additionally be fused,
where the heterocycle and/or the fused-on groups may each, independently
of one another, bear one, two, three or four substituents selected from
among alkyl, alkoxy, halogen, nitro, cyano, carboxyl, SO.sub.3 H,
sulfonate, NE.sup.4 E.sup.5, alkylene-NE.sup.4 E.sup.5 and carboxylate.
The radicals Y.sup.1 and Y.sup.2 are preferably selected from among
phosphonite and/or phosphite radicals of the formula II
##STR2##
where
r, s and t are each, independently of one another, 0 or 1 and the sum of r,
s and t is at least 2,
D together with the phosphorus atom and the oxygen atom(s) to which it is
bound form a 5- to 8-membered heterocycle to which one, two or three
cycloalkyl, heterocycloalkyl, aryl and/or hetaryl groups may be fused,
where the fused-on groups may each bear, independently of one another,
one, two, three or four substituents selected from among alkyl, alkoxy,
halogen, SO.sub.3 H, sulfonate, NE.sup.4 E.sup.5, alkylene-NE.sup.4
E.sup.5, nitro, cyano, carboxyl and carboxylate, and/or D may have one,
two or three substituents selected from among alkyl, alkoxy, substituted
or unsubstituted cycloalkyl and substituted or unsubstituted aryl, and/or
D may be interrupted by 1, 2 or 3 substituted or unsubstituted hetero
atoms.
The radical D is preferably a C.sub.2 -C.sub.6 -alkylene bridge to which 1
or 2 aryl groups are fused and/or may have a substituent selected from
among alkyl, substituted or unsubstituted cycloalkyl and substituted or
unsubstituted aryl, and/or may be interrupted by a substituted or
unsubstituted hetero atom.
The fused-on arylene of the radical D is preferably benzene or naphthalene.
Fused-on benzene rings are preferably unsubstituted or have 1, 2 or 3, in
particular 1 or 2, substituents selected from among alkyl, alkoxy,
halogen, SO.sub.3 H, sulfonate, NE.sup.4 E.sup.5, alkylene-NE.sup.4
E.sup.5, trifluoromethyl, nitro, carboxyl, alkoxycarbonyl, acyl and cyano.
Fused-on naphthalenes are preferably unsubstituted or have 1, 2 or 3, in
particular 1 or 2, of the substituents mentioned above for the fused-on
benzene rings in the ring which is not fused on and/or in the fused-on
ring. An alkyl substituent on the fused-on aryls is preferably C.sub.1
-C.sub.4 -alkyl and in particular methyl, isopropyl or tert-butyl. Alkoxy
is preferably C.sub.1 -C.sub.4 -alkoxy and in particular methoxy.
Alkoxycarbonyl is preferably C.sub.1 -C.sub.4 -alkoxycarbonyl. Halogen is
particularly preferably fluorine or chlorine.
If the C.sub.2 -C.sub.6 -alkylene bridge of the radical D is interrupted by
1, 2 or 3 substituted or unsubstituted hetero atoms, these are preferably
selected from among O, S and NR.sup.h, where R.sup.h is alkyl, cycloalkyl
or aryl. The C.sub.2 -C.sub.6 -alkylene bridge of the radical D is
preferably interrupted by one substituted or unsubstituted hetero atom.
If the C.sub.2 -C.sub.6 -alkylene bridge of the radical D is substituted,
it preferably has 1, 2 or 3, in particular 1, substituents selected from
among alkyl, cycloalkyl and aryl, where the aryl substituent may bear 1, 2
or 3 of the substituents mentioned for aryl. The alkylene bridge D
preferably has one substituent selected from among methyl, ethyl,
isopropyl, phenyl, p-(C.sub.1 -C.sub.4 -alkyl)phenyl, preferably
p-methylphenyl, p-(C.sub.1 -C.sub.4 -alkoxy)phenyl, preferably
p-methoxyphenyl, p-halophenyl, preferably p-chlorophenyl, and
p-trifluoromethylphenyl.
The radical D is preferably a C.sub.3 -C.sub.6 -alkylene bridge which is
fused and/or substituted and/or interrupted by substituted or
unsubstituted hetero atoms as described above. In particular, the radical
D is a C.sub.3 -C.sub.6 -alkylene bridge on to which one or two phenyl
and/or naphthyl groups are fused, where the phenyl or naphthyl groups may
bear 1, 2 or 3, in particular 1 or 2, of the abovementioned substituents.
Preference is given to the radical D (i.e. R.sup.7 and R.sup.8 together)
together with the phosphorus atom and the oxygen atom(s) to which it is
bound forming a 5- to 8-membered heterocycle, with the radical D (R.sup.7
and R.sup.8 together) being a radical selected from among the radicals of
the formulae II.1 to II.5,
##STR3##
where
z is O, S or NR.sup.i, where
R.sup.i is alkyl, cycloalkyl or aryl,
or Z is a C.sub.1 -C.sub.3 -alkylene bridge which may have a double bond
and/or an alkyl, cycloalkyl or aryl substituent, where the aryl
substituent may bear one, two or three of the substituents mentioned for
aryl,
or Z is a C.sub.2 -C.sub.3 -alkylene bridge which is interrupted by O, S or
NR.sup.i,
R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15 and
R.sup.16 are each, independently of one another, hydrogen, alkyl,
cycloalkyl, aryl, alkoxy, halogen, SO.sub.3 H, sulfonate, NE.sup.4
E.sup.5, alkylene-NE.sup.4 E.sup.5, trifluoromethyl, nitro,
alkoxycarbonyl, carboxyl or cyano.
D is preferably a radical of the formula II.1 in which R.sup.9 and R.sup.10
are each hydrogen.
D is preferably a radical of the formula II.2a
##STR4##
where
R.sup.9 is hydrogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy,
SO.sub.3 H, sulfonate, NE.sup.4 E.sup.5, alkylene-NE.sup.4 E.sup.5,
preferably hydrogen, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy,
in particular methyl, methoxy, isopropyl or tert-butyl,
R.sup.10 is hydrogen, C.sub.1 -C.sub.4 -alkyl, preferably methyl, isopropyl
or tert-butyl, C.sub.1 -C.sub.4 -alkoxy, preferably methoxy, fluorine,
chlorine or trifluoromethyl. R.sup.10 may also be SO.sub.3 H, sulfonate,
NE.sup.4 E.sup.5 or alkylene-NE.sup.4 E.sup.5.
D is prefeably a radical of the formula II.3a
##STR5##
where
R.sup.9 and R.sup.10 are as defined for the formula II.2a,
R.sup.1 is hydrogen, C.sub.1 -C.sub.4 -alkyl, preferably methyl or ethyl,
phenyl, p-(C.sub.1 -C.sub.4 -alkoxy)phenyl, preferably p-methoxyphenyl,
p-fluorophenyl, p-chlorophenyl or p-(trifluoromethyl)phenyl.
D is preferably a radical of the formula II.4 in which R.sup.9, R.sup.10,
R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15 and R.sup.16 are each
hydrogen.
D is preferably a radical of the formula II.4 in which R.sup.9, R.sup.10,
R.sup.11, R.sup.12, R.sup.14 and R.sup.16 are each hydrogen and the
radicals R.sup.13 and R.sup.15 are each, independently of one another,
alkoxycarbonyl, preferably methoxycarbonyl, ethoxycarbonyl,
n-propyloxycarbonyl or isopropyloxycarbonyl. In particular, the radicals
R.sup.13 and R.sup.15 are located in the ortho position relative to the
phosphorus atom or oxygen atom.
D is preferably a radical of the formula II.5 in which R.sup.9, R.sup.10,
R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15 and R.sup.16 are each
hydrogen and Z is CR.sup.l, where R.sup.1 is as defined above.
D is preferably a radical of the formula II.5 in which R.sup.9, R.sup.10,
R.sup.11, R.sup.12, R.sup.14 and R.sup.16 are each hydrogen, Z is CR.sup.h
and the radicals R.sup.13 and R.sup.15 are each, independently of one
another, alkoxycarbonyl, preferably methoxycarbonyl, ethoxycarbonyl,
n-propyloxycarbonyl or isopropyloxycarbonyl. In particular, the radicals
R.sup.13 and R.sup.15 are located in the ortho position relative to the
phosphorus atom or oxygen atom.
In a further, preferred embodiment, one of the radicals Y.sup.1 or Y.sup.2
or both radicals Y.sup.1 and Y.sup.2 in the formula I are selected from
among radicals of the formulae P(OR.sup.7)(OR.sup.8), OP(OR.sup.7)R.sup.8
and OP(OR.sup.7)(OR.sup.8) in which R.sup.7 and R.sup.8 do not together
form a heterocycle.
The radicals R.sup.7 and R.sup.8 are preferably each, independently of one
another, alkyl, aryl or hetaryl which may bear one, two or three
substituents selected from among alkyl (only for aryl or hetaryl),
cycloalkyl, aryl, alkoxy, cycloalkoxy, aryloxy, halogen, trifluoromethyl,
nitro, cyano, carboxyl, carboxylate, acyl, --SO.sub.3 H, sulfonate,
NE.sup.4 E.sup.5 and alkylene-NE.sup.4 E.sup.5, where E.sup.4 and E.sup.5
are identical or different and are selected from among alkyl, cycloalkyl
and aryl.
The radicals R.sup.7 and R.sup.8 are preferably selected independently from
among the radicals of the formulae II.6 and II.7
##STR6##
where
R.sup.9 and R.sup.10 are each, independently of one another, hydrogen,
C.sub.1 -C.sub.4 -alkyl, COOR.sup.f, COO.sup.- M.sup.+, SO.sub.3 R.sup.d,
SO.sub.3.sup.- M.sup.+, NE.sup.4 E.sup.5, alkylene-NE.sup.4 E.sup.5,
NE.sup.4 E.sup.5 E.sup.6+ X.sup.-, alkylene-NE.sup.4 E.sup.5 E.sup.6+
X.sup.-, C.sub.1 -C.sub.4 -alkoxy, halogen or trifluoromethyl, where
R.sup.f, E.sup.4, E.sup.5 and E.sup.6 may be identical or different and
are each hydrogen, alkyl, cycloalkyl or aryl, M.sup.+ is a cation and
X.sup.- is an anion.
In the formulae II.6 and II.7, the radicals R.sup.9 and R.sup.10 are
preferably each, independently of one another, hydrogen, C.sub.1 -C.sub.4
-alkyl or C.sub.1 -C.sub.4 -alkoxy, in particular methyl, methoxy,
isopropyl or tert-butyl.
A.sup.1 and A.sup.2 are preferably each, independently of one another, O, S
and CR.sup.5 R.sup.6, where R.sup.5 and R.sup.6 are each, independently of
one another, hydrogen, alkyl, cycloalkyl, aryl or hetaryl. In particular,
R.sup.5 and R.sup.6 are each, independently of one another, hydrogen or
C.sub.1 -C.sub.4 -alkyl such as methyl, ethyl, n-propyl, n-butyl or
tert-butyl. In particular, R.sup.5 and R.sup.6 are both methyl.
Preference is given to one of the radicals A.sup.1 or A.sup.2 being O or S
and the other being CR.sup.5 R.sup.6. More preferably, the radicals
A.sup.1 and A.sup.2 are selected from among O and S.
The radicals R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are preferably selected
from among hydrogen, alkyl, cycloalkyl, aryl and hetaryl. Preference is
given to R.sup.1 and R.sup.3 being hydrogen and R.sup.2 and R.sup.4 being
C.sub.1 -C.sub.4 -alkyl such as methyl, ethyl, n-propyl, n-butyl or
tert-butyl.
At least one of the radicals R.sup.1, R.sup.2, R.sup.3 and/or R.sup.4 is
preferably a polar (hydrophilic) group, which then generally results in
water-soluble catalysts. The polar groups are preferably selected from
among COOR.sup.d, COO.sup.- M.sup.+, SO.sub.3 R.sup.d, SO.sup.-.sub.3
M.sup.+, NE.sup.1 E.sup.2, alkylene-NE.sup.1 E.sup.2, NE.sup.1 E.sup.2
E.sup.3+ X.sup.-, alkylene-NE.sup.1 E.sup.2 E.sup.3+ X.sup.-, OR.sup.d,
SR.sup.d, (CHR.sup.e CH.sub.2 O).sub.x R.sup.d or (CH.sub.2 CH.sub.2
N(E.sup.1)).sub.x R.sup.d, where R.sup.d, E.sup.1, E.sup.2, E.sup.3,
R.sup.d, R.sup.e, M.sup.+, X.sup.- and x are as defined above.
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are particularly preferably each
hydrogen.
If R.sup.1 and/or R.sup.3 form a fused-on ring system, the fused-on groups
are preferably benzene or naphthalene groups. Fused-on benzene rings are
preferably unsubstituted or have 1, 2 or 3, in particular 1 or 2,
substituents selected from among alkyl, alkoxy, halogen, SO.sub.3 H,
sulfonate, NE.sup.4 E.sup.5, alkylene-NE.sup.4 E.sup.5, trifluoromethyl,
nitro, carboxyl, alkoxycarbonyl, acyl and cyano. Fused-on naphthalenes are
preferably unsubstituted or have 1, 2, or 3, in particular 1 or 2, of the
substituents mentioned above for the fused-on benzene rings in the ring
which is not fused on and/or in the fused-on ring.
M.sup.+ is preferably an alkali metal cation, e.g. Li.sup.+, Na.sup.+ or
K.sup.+, NH.sub.4.sup.+ or a quarternary ammonium compound as is
obtainable by protonation or quaternization of amines.
X.sup.- is preferably halide, particularly preferably Cl.sup.- or Br.sup.-.
In a preferred embodiment of the process of the present invention, use is
made of a hydroformylation catalyst in which the compound of the formula I
is selected from among the compounds of the formulae I.1 to I.6
##STR7##
##STR8##
where
A.sup.1 is O, S or CR.sup.5 R.sup.6, where R.sup.5 and R.sup.6 are each,
independently of one another, hydrogen or C.sub.1 -C.sub.4 -alkyl, in
particular methyl or tert-butyl,
R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22, R.sup.23 and
R.sup.24 are each, independently of one another,
hydrogen, alkyl, preferably C.sub.1 -C.sub.4 -alkyl, in particular methyl
or tert-butyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, COOR.sup.d,
COO.sup.- M.sup.+, SO.sub.3 R.sup.f, SO.sup.-.sub.3 M.sup.+, NE.sup.4
E.sup.5, alkylene-NE.sup.4 E.sup.5, NE.sup.4 E.sup.5 E.sup.6+ X.sup.-,
alkylene-NE.sup.4 E.sup.5 E.sup.6+ X.sup.-, OR.sup.f, preferably C.sub.1
-C.sub.4 -alkoxy, in particular methoxy, SR.sup.f, (CHR.sup.g CH.sub.2
O).sub.y R.sup.f, (CH.sub.2 N(E.sup.4)).sub.y R.sup.f, (CH.sub.2 CH.sub.2
N(E.sup.4)).sub.y R.sup.f, halogen, trifluoromethyl, nitro, acyl and
cyano,
where
R.sup.f, E.sup.4, E.sup.5 and E.sup.6 are identical or different radicals
selected from among hydrogen, alkyl, preferably C.sub.1 -C.sub.4 -alkyl,
in particular methyl or tert-butyl, alkoxy, preferably methoxy, cycloalkyl
and aryl,
R.sup.g is hydrogen, methyl or ethyl,
M.sup.+ is a cation,
X.sup.- is an anion, and
y is an integer from 1 to 120.
The invention further provides compounds of the formula I
##STR9##
where
A.sup.1 and A.sup.2 are each, independently of one another, O, S, SiR.sup.a
R.sup.b, NR.sup.c or CR.sup.5 R.sup.6, with the exception of A.sup.1 =S
and A.sup.2 =O, where
R.sup.a, R.sup.b, R.sup.c, R.sup.5 and R.sup.6 are each, independently of
one another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or
hetaryl,
Y.sup.1 and Y.sup.2 are each, independently of one another, radicals
containing at least one phosphorus, arsenic or antimony atom, where in
each case at least two substituted or unsubstituted heteroatoms selected
from among O, S and NR.sup.c, where R.sup.c is hydrogen, alkyl, cycloalkyl
or aryl, are directly bound to the phosphorus, arsenic or antimony atom,
and
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each, independently of one
another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl,
COOR.sup.d, COO.sup.- M.sup.+, SO.sub.3 R.sup.d, SO.sup.-.sub.3 M.sup.+,
NE.sup.1 E.sup.2, NE.sup.1 E.sup.2 E.sup.3+ X.sup.-, alkylene-NE.sup.1
E.sup.2 E.sup.3+ X.sup.-, OR.sup.d, SR.sup.d, (CHR.sup.e CH.sub.2 O).sub.x
R.sup.d, (CH.sub.2 N(E.sup.1)).sub.x R.sup.d, (CH.sub.2 CH.sub.2
N(E.sup.1)).sub.x R.sup.d, halogen, trifluoromethyl, nitro, acyl or cyano,
where
R.sup.d, E.sup.1, E.sup.2 and E.sup.3 are identical or different radicals
selected from among hydrogen, alkyl, cycloalkyl and aryl,
R.sup.e is hydrogen, methyl or ethyl,
M.sup.+ is a cation,
X.sup.- is an anion, and
x is an integer from 1 to 120, or
R.sup.1 and/or R.sup.3 together with two adjacent carbon atoms of the
benzene ring to which they are bound form a fused ring system having 1, 2
or 3 further rings.
As regards preferred embodiments of the compounds of the formula I,
reference may be made to what has been said above in respect of the
ligands of the formula I used in the hydroformylation process of the
present invention.
The invention further provides a catalyst comprising at least one complex
of a metal of transition group VIII with at least one novel compound of
the formula I as defined above.
The catalysts of the present invention and those used according to the
present invention may comprise one or more of the compounds of the formula
I as ligands. In addition to the above-described ligands of the formula I,
they may further comprise at least one additional ligand selected from
among halides, amines, carboxylates, acetylacetonate, arylsulfonates and
alkylsulfonates, hydride, CO, olefins, dienes, cycloolefins, nitriles,
N-containing heterocycles, aromatics and heteroaromatics, ethers,
PF.sub.3, phospholes, phosphabenzenes and monodentate, bidentate and
polydentate phosphine, phosphinite, phosphonite, phosphoramidite and
phosphite ligands.
The metal of transition group VIII is preferably cobalt, ruthenium,
rhodium, palladium, platinum, osmium or iridium, in particular cobalt,
rhodium, ruthenium or iridium.
The preparation of the compounds of the formula I used according to the
present invention and the novel compounds of the formula I can be carried
out, for example, starting from a compound of the formula I.a
##STR10##
where
Y.sup.a and Y.sup.b are each, independently of one another, a radical
Y.sup.1 or Y.sup.2 as defined above, or Y.sup.a and Y.sup.b are each,
independently of one another, halogen, OH, OC(O)CF.sub.3 or SO.sub.3 Me
where Me=hydrogen, Li, Na or K, and Y.sup.a and/or Y.sup.b may also be
hydrogen if at least one of the radicals R.sup.2 and/or R.sup.4 is
hydrogen, an alkoxy group or an alkoxycarbonyl group located in the ortho
position relative to Y.sup.a and/or Y.sup.b, and
A.sup.1, A.sup.2, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are as defined
above.
The functionalization of the radicals Y.sup.a and Y.sup.b to form the
radicals Y.sup.1 and Y.sup.2 can be carried out in a manner analogous to
known methods. For example, compounds of the formula I.a in which Y.sup.a
and Y.sup.b are halogen, preferably chlorine, can firstly be lithiated and
the intermediate formed can be reacted with a compound which bears a
halogen atom, preferably a chlorine atom, on the phosphorus atom, for
example a compound of the formula Cl-P(OR.sup.7).sub.2,
Cl-P(OR.sup.7)(OR.sup.8) or Cl-P(OR.sup.7).sub.2. The novel compounds I in
which Y.sup.1 and Y.sup.2 are each a radical of the formula II in which
t=0 are prepared by, for example, reaction of I.a with compounds of the
formula II.a according to the following scheme,
##STR11##
where r, s and D are as defined above for the compounds of the formula II.
In place of compounds of the formula I.a in which Y.sup.a =Y.sup.b
=halogen, it is also possible to lithiate compounds I.a in which Y.sup.a
=Y.sup.b =hydrogen and in which hydrogen, an alkoxy group or an
alkoxycarbonyl group is present in each of the ortho positions relative to
Y.sup.a and Y.sup.b. Such reactions are described in the literature under
the name "Ortho-Lithiation" (see, for example, D. W. Slocum, J. Org.
Chem., 1976, 41, 3652-3654; J. M. Mallan, R. L. Bebb, Chem. Rev., 1969,
693 ff; V. Snieckus, Chem. Rev., 1980, 6, 879-933). The organolithium
compounds obtained in this way can then be reacted with the phosphorus
halide compounds in the manner indicated above to form the target
compounds I.
The arsenic compounds I and the antimony compounds I can be prepared in an
analogous way.
In general, the catalysts or catalyst precursors used in each case are
converted under hydroformylation conditions into catalytically active
species of the formula H.sub.x M.sub.y (CO).sub.z L.sub.q, where M is a
metal of transition group VIII, L is a phosphorus-, arsenic- or
antimony-containing compound of the formula I and q, x, y, z are integers
which depend on the valence and type of the metal and also the number of
coordination positions occupied by the ligand L. z and q are preferably,
independently of one another, at least 1, e.g. 1, 2 or 3. The sum of z and
q is preferably from 2 to 5. If desired, the complexes may further
comprise at least one of the above-described additional ligands.
In a preferred embodiment, the hydroformylation catalysts are prepared in
situ in the reactor used for the hydroformylation reaction. However, if
desired, the catalysts used according to the present invention can also be
prepared separately and isolated by customary methods. To prepare the
catalysts used according to the present invention in situ, it is possible,
for example, to react at least one compound of the formula I, a compound
or a complex of a metal of transition group VIII, if desired at least one
further additional ligand and, if desired, an activating agent in an inert
solvent under the hydroformylation conditions.
Suitable rhodium compounds or complexes are, for example, rhodium(II) and
rhodium(III) salts, e.g. rhodium(III) chloride, rhodium(III) nitrate,
rhodium(III) sulfate, potassium rhodium sulfate, rhodium(II) and
rhodium(III) carboxylates, rhodium(II) and rhodium(III) acetate,
rhodium(III) oxide, salts of rhodic(III) acid, trisammonium
hexachlororhodate(III), etc. Also suitable are rhodium complexes such as
dicarbonylrhodium acetylacetonate, acetylacetonatobisethylenerhodium(I),
etc. Preference is given to using dicarbonylrhodium acetylacetonate or
rhodium acetate.
Ruthenium salts or compounds are likewise suitable. Suitable ruthenium
salts are, for example, ruthenium(III) chloride, ruthenium(IV),
ruthenium(VI) or ruthenium(VIII) oxide, alkali metal salts of ruthenium
oxo acids such as K.sub.2 RuO.sub.4 or KRuO.sub.4 or complexes such as
RuHCl(CO)(PPh.sub.3).sub.3. It is also possible to use the carbonyls of
ruthenium, e.g. dodecacarbonyltriruthenium or
octadecacarbonylhexaruthenium, or mixed forms in which Co has been
partially replaced by ligands of the formula PR.sub.3, e.g. Ru(CO).sub.3
(PPh.sub.3).sub.2, in the process of the present invention.
Suitable cobalt compounds are, for example cobalt(II) chloride, cobalt(II)
sulfate, cobalt(II) carbonate, cobalt(II) nitrate, their amine or hydrate
complexes, cobalt carboxylates such as cobalt acetate, cobalt
ethylhexanoate, cobalt naphthanoate, and also the caprolactamate complex
of cobalt. Here too, the carbonyl complexes of cobalt, e.g.
octacarbonyldicobalt, dodecacarbonyltetracobalt and
hexadecacarbonylhexacobalt, can be used.
The abovementioned and further suitable compounds of cobalt, rhodium,
ruthenium and iridium are known in principle and are adequately described
in the literature or they can be prepared by a person skilled in the art
using methods analogous to those for known compounds.
Suitable activating agents are, for example, Bronsted acids, Lewis acids,
e.g. BF.sub.3, AlCl.sub.3, ZnCl.sub.2, and Lewis bases.
As solvents, preference is given to using the aldehydes which are formed in
the hydroformylation of the respective olefins, and also their
higher-boiling downstream reaction products, e.g. the products of the
aldol condensation. Further suitable solvents are aromatics such as
toluene and xylenes, hydrocarbons or mixtures of hydrocarbons, also for
dilution of the abovementioned aldehydes and the downstream products of
the aldehydes. Further solvents are esters of aliphatic carboxylic acids
with alkanoles, for example ethyl acetate or Texanol.TM., ethers such as
tert-butyl methyl ether and tetrahydrofuran. In the case of sufficiently
hydrophilic ligands, it is also possible to use alcohols such as methanol,
ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ketones, such as
acetone and methyl ethyl ketone etc.
"Ionic liquids" can also be used as solvents. These are liquid salts, for
example N,N'-dialkylimidazolium salts such as N-butyl-N'-methylimidazolium
salts, tetraalkylammonium salts such as tetra-n-butylammonium salts,
N-alkylpyridinium salts such as n-butylpyridinium salts,
tetraalkylphosphonium salts such as trishexyl(tetradecyl)phosphonium
salts, e.g. the tetrafluoroborates, acetates, tetrachloroaluminates,
hexafluorophosphates, chlorides and tosylates.
Furthermore, the reactions can also be carried out in water or aqueous
solvent systems comprising water together with a water-miscible solvent,
for example an alcohol such as methanol, ethanol, n-propanol, isopropanol,
n-butanol, isobutanol, a ketone such as acetone or methyl ethyl ketone or
another solvent. For this purpose, use is made of ligands of the formula I
which have been modified with polar groups, for example ionic groups such
as SO.sub.3 Me, CO.sub.2 Me where Me=Na, K or NH.sub.4, or such as
N(CH.sub.3).sub.3.sup.+. The reactions then occur as a two-phase catalysis
in which the catalyst is present in the aqueous phase and starting
materials and products form the organic phase. The reaction in the "ionic
liquids" can also be carried out as a two-phase catalysis.
The molar ratio of phosphorus-containing ligand to metal of transition
group VIII is generally in a range from about 1:1 to 1000:1.
Suitable substrates for the hydroformylation process of the present
invention are in principle all compounds which contain one or more
ethylenically unsaturated double bonds. These include, for example,
olefins such as .alpha.-olefins, internal straight-chain and internal
branched olefins. Suitable .alpha.-olefins are, for example, ethylene,
propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,
1-decene, 1-undecene, 1-dodecene, etc.
Preferred branched, internal olefins are C.sub.4 -C.sub.20 -olefins such as
2-methyl-2-butene, 2-methyl-2-pentene, 3-methyl-2-pentene, branched,
internal heptene mixtures, branched, internal octene mixtures, branched,
internal nonene mixtures, branched, internal decene mixtures, branched,
internal undecene mixtures, branched, internal dodecene mixtures, etc.
Further suitable olefins for the hydroformylation are C.sub.5 -C.sub.8
-cycloalkenes such as cyclopentene, cyclohexene, cycloheptene, cyclooctene
and their derivatives, e.g. their C.sub.1 -C.sub.20 -alkyl derivatives
having from 1 to 5 alkyl substituents. Olefins suitable for
hydroformylation also include vinyl aromatics such as styrene,
.alpha.-methylstyrene, 4-isobutylstyrene, etc. Other suitable olefins for
the hydroformylation are .alpha.,.beta.-ethylenically unsaturated
monocarboxylic and/or dicarboxylic acids, their esters, monoesters and
amides, e.g. acrylic acid, methacrylic acid, maleic acid, fumaric acid,
crotonic acid, itaconic acid, methyl 3-penteneoate, methyl 4-penteneoate,
methyl oleate, methyl acrylate, methyl methacrylate, unsaturated nitriles
such as 3-pentenenitrile, 4-pentenenitrile, acrylonitrile, vinyl ethers
such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc.,
C.sub.1 -C.sub.20 -alkenols, -alkenediols and -alkadienoles, e.g.
2,7-octadien-1-ol. Further suitable substrates are dienes or polyenes
containing isolated or conjugated double bonds. These include, for
example, 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene,
1,7-octadiene, vinylcyclohexene, dicyclopentadiene, 1,5,9-cyclooctatriene
and also homopolymers and copolymers of butadiene.
The unsaturated compound used for the hydroformylation is preferably
selected from among internal linear olefins and olefin mixtures in which
at least one internal linear olefin is present. Preferred linear
(straight-chain) internal olefins are C.sub.4 -C.sub.20 -olefins such as
2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene,
3-octene, 4-octene, etc., and mixtures thereof.
In the hydroformylation process of the present invention, preference is
given to using an olefin mixture which is available on an industrial scale
and comprises, in particular, at least one internal linear olefin. These
include, for example, the Ziegler olefins obtained by controlled ethene
oligomerization in the presence of alkylaluminum catalysts. These are
essentially unbranched olefins having a terminal double bond and an even
number of carbon atoms. Further examples are the olefins obtained by
ethene oligomerization in the presence of various catalyst systems, e.g.
the predominantly linear .alpha.-olefins obtained in the presence of
alkylaluminum chloride/titanium tetrachloride catalysts and the
.alpha.-olefins obtained by the Shell Higher Olefin Process (SHOP) in the
presence of nickel-phosphine complexes as catalysts. Further suitable
industrially available olefin mixtures are obtained in the paraffin
dehydrogenation of appropriate petroleum fractions, e.g. kerosene or
diesel oil fractions. To convert paraffins, predominantly n-paraffins,
into olefins, essentially three processes are used:
thermal cracking (steam cracking),
catalytic dehydrogenation and
chemical dehydrogenation by chlorination and dehydrochlorination.
Thermal cracking leads predominantly to .alpha.-olefins, while the other
variants produce olefin mixtures which generally also have relatively high
proportions of olefins containing an internal double bond. Further
suitable olefin mixtures are the olefins obtained in metathesis or
telomerization reactions. They include, for example, the olefins from the
Phillips triolefin process, a modified SHOP comprising ethylene
oligomerization, double bond isomerization and subsequent metathesis
(ethenolysis).
Further suitable industrial olefin mixtures which can be used in the
hydroformylation process of the present invention are selected from among
dibutenes, tributenes, tetrabutenes, dipropenes, tripropenes,
tetrapropenes, mixtures of butene isomers, in particular raffinate II,
dihexenes, dimers and oligomers from the Dimersol.RTM. process of IFP, the
Octol.RTM. process of Huls, the Polygas process, etc.
Preference is given to a process in which the hydroformylation catalyst is
prepared in situ by reacting at least one compound of the formula I, a
compound or a complex of a metal of transition group VIII and, if desired,
an activating agent in an inert solvent under the hydroformylation
conditions.
The hydroformylation reaction can be carried out continuously,
semicontinuously or batchwise.
Suitable reactors for the continuous reaction are known to those skilled in
the art and are described, for example, in Ullmanns Enzyklopadie der
technischen Chemie, Vol. 1, 3rd Edition, 1951, p. 743 ff.
Suitable pressure-rated reactors are likewise known to those skilled in the
art and are described, for example, in Ullmanns Enzyklopadie der
technischen Chemie, Vol. 1, 3rd Edition, 1951, p. 769 ff. In general, the
process of the present invention is carried out using an autoclave which
may, if desired, be provided with a stirrer and an internal lining.
The composition of the synthesis gas comprising carbon monoxide and
hydrogen used in the process of the present invention can vary within a
wide range. The molar ratio of carbon monoxide to hydrogen is generally
from about 5:95 to 70:30, preferably from about 40:60 to 60:40. Particular
preference is given to using a molar ratio of carbon monoxide to hydrogen
in the region of about 1:1.
The temperature in the hydroformylation reaction is generally in a range
from about 20 to 180.degree. C., preferably from about 50 to 150.degree.
C. The reaction is generally carried out at the partial pressure of the
reaction gas at the reaction temperature chosen. The pressure is generally
in a range from about 1 to 700 bar, preferably from 1 to 600 bar, in
particular from 1 to 300 bar. The reaction pressure can be varied as a
function of the activity of the hydroformylation catalyst used. In
general, the catalysts based on phosphorus-, arsenic- or
antimony-containing compounds which are used according to the present
invention allow reaction in a low pressure range, for example in the range
from 1 to 100 bar.
The hydroformylation catalysts of the present invention and those used
according to the present invention can be separated from the output from
the hydroformylation reaction by customary methods known to those skilled
in the art and can generally be reused for the hydroformylation.
The above-described novel catalysts which comprise chiral compounds of the
formula I are suitable for enantioselective hydroformylation.
The above-described catalysts can also be immobilized on a suitable
support, e.g. made of glass, silica gel, synthetic resins, etc., in a
suitable manner, e.g. by binding via functional groups suitable as anchor
groups, adsorption, grafting, etc. They are then also suitable for use as
solid-phase catalysts.
Surprisingly, the hydroformylation activity of catalysts based on phosphine
ligands of the formula I is generally higher than the activity in respect
of isomerization to form internal double bonds. The catalysts of the
present invention and those used according to the present invention
advantageously display a high selectivity to .alpha.-aldehydes or
.alpha.-alcohols in the hydroformylation of .alpha.-olefins. In addition,
the hydroformylation of internal linear olefins (isomerizing
hydroformylation) generally also gives good yields of .alpha.-aldehydes or
-alcohols and in particular n-aldehydes or -alcohols. Furthermore, these
catalysts generally have a high stability under hydroformylation
conditions, so that they generally make it possible to achieve longer
catalyst operating lives than are achieved using the catalysts based on
conventional chilating ligands known from the prior art. Furthermore, the
catalysts of the present invention and those used according to the present
invention advantageously display a high activity, so that the
corresponding aldehydes or alcohols are generally obtained in good yields.
In the hydroformylation of .alpha.-olefins and also of internal, linear
olefins, they also display a very low selectivity to the hydrogenation
product of the olefin used.
The invention further provides for the use of catalysts comprising at least
one complex of a metal of transition group VIII with at least one compound
of the formula I, as described above, for hydroformylation, carbonylation
and hydrogenation.
The invention is illustrated by the nonrestrictive examples below.
EXAMPLES
The following li
