U.S. patent application number 10/292657 was filed with the patent office on 2003-08-07 for valeraldehyde and process for its preparation.
This patent application is currently assigned to Celanese GmbH. Invention is credited to Geissler, Holger, Kamer, Paul C.J., Leeuwen, Petrus W.N.M. Van, Van der Veen, Lars A..
Application Number | 20030149267 10/292657 |
Document ID | / |
Family ID | 7878746 |
Filed Date | 2003-08-07 |
United States Patent
Application |
20030149267 |
Kind Code |
A1 |
Geissler, Holger ; et
al. |
August 7, 2003 |
Valeraldehyde and process for its preparation
Abstract
Bidentate phosphine ligands of the formula 1 wherein the
substituents are as defined in the specification and a process for
preparing linear aldehydes by hydroformylating internal olefins
using such phosphine ligands.
Inventors: |
Geissler, Holger; (Mainz,
DE) ; Leeuwen, Petrus W.N.M. Van; ( Kockengen,
NL) ; Kamer, Paul C.J.; (Naarden, NL) ; Van
der Veen, Lars A.; (Amsterdam, NL) |
Correspondence
Address: |
MUSERLIAN AND LUCAS AND MERCANTI, LLP
600 THIRD AVENUE
NEW YORK
NY
10016
US
|
Assignee: |
Celanese GmbH
|
Family ID: |
7878746 |
Appl. No.: |
10/292657 |
Filed: |
November 12, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10292657 |
Nov 12, 2002 |
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10014756 |
Nov 13, 2001 |
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10014756 |
Nov 13, 2001 |
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09376909 |
Aug 18, 1999 |
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6342605 |
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Current U.S.
Class: |
546/2 ; 556/16;
556/18; 568/12; 568/451 |
Current CPC
Class: |
B01J 31/2471 20130101;
C07C 45/50 20130101; C07F 9/65683 20130101; C07F 9/657163 20130101;
B01J 2531/822 20130101; B01J 31/2438 20130101; C07C 45/50 20130101;
C07C 47/02 20130101 |
Class at
Publication: |
546/2 ; 556/16;
556/18; 568/12; 568/451 |
International
Class: |
C07F 015/00; C07F
017/02; C07F 009/28; C07C 045/49 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 26, 1998 |
DE |
198 38 742.3 |
Claims
What we claim is:
1. A bidentate phosphine ligand of the formula 13wherein R1, R2, R3
and R4 are independently selected from the group consisting of
hydrogen, fluorine, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8
carbon atoms, acyloxy of an organic carboxylic acid of 1 to 8
carbon atoms, aryl of 6 to 18 carbon atoms, aryloxy of 6 to 18
carbon atoms, --CN, --CF.sub.3, --CHO, --SO.sub.3H, --SO.sub.3M,
--SO.sub.3R, --SOR, --NH.sub.2, --NH-alkyl of 1 to 8 carbon atoms,
--N-alkyl.sub.2 of 1 to 8 carbon atoms, --NHCO-alkyl,
--N-(alkyl)-(CO-(alkyl) where the alkyl have 1 to 4 carbon atoms,
--COO-alkyl of 1 to 8 carbon atoms, --CONH.sub.2, --CO-alkyl of 1
to 8 carbon atoms, --NHCOH, --NHCOO-alkyl of 1 to 4 carbon atoms,
--CO-aryl of 1 to 8 carbon atoms, --COO-aryl of 1 to 8 carbon
atoms, --CHCH--CO.sub.2-alkyl of 1 to 8 carbon atoms,
--PO-(-aryl).sub.2 of 1 to 8 carbon atoms, --PO-(alkyl.sub.2) of 1
to 4 carbon atoms; M is a cation selected from the group consisting
of alkali metal ions, alkaline earth metal ions, --NR.sub.2H.sub.2,
--NR.sub.3H, --NRH.sub.3, --NR.sub.4, --NH.sub.4,
--PR.sub.2H.sub.2, --PR.sub.3H, --PRH.sub.3, --PR.sub.4 and
--PH.sub.4; or R1, R2, R3 and R4, with one another, together form
at least one aliphatic or aromatic ring of 5 to 20 carbon atoms; E
is a bridge linking the two phosphorus atoms, where the number of
atoms situated between the two phosphorus atoms is 2 and 6,
selected from the group consisting of C, N, Si, S, 0, P, Fe and As;
X is selected from the group consisting of --O--, --S--,
--Si(R.sup.a).sub.2--, --Si(OR.sup.a).sub.2--, --N(C(O)R.sup.a)--,
--N(R.sup.b)--, --C(R.sup.c)(R.sup.c), --C(O)--, --N(SiR.sup.d)--,
--P(R.sup.d)--, P(O)(R.sup.d)--, --C.dbd.C(R.sup.c)(R.sup.c)-- and
--P(OR.sup.d)-- wherein R.sup.a is alkyl of 1 to 8 carbon atoms,
R.sup.b is aryl of 6 to 18 carbon atoms, R.sup.c is selected from
the group consisting of hydrogen, alkyl of 1 to 8 carbon atoms,
aryl of 6 to 18 carbon atoms, alkoxy of 1 to 8 carbon atoms,
aryloxy of 6 to 18 carbon atoms, R.sup.a(O)-- and R.sup.b(o); and
R.sup.d is one of R.sup.a or R.sup.b.
2. The ligand of claim 1 wherein E is selected from the group
consisting of 14wherein X is selected from the group consisting of
--O--, --S--, --Si(R.sup.a).sub.2--, --Si(OR.sup.a).sub.2--,
--N(C(O)R.sup.a)--, --N(R.sup.b)--, --C(R.sup.c)(R.sup.c)--,
--C(O)--, --N(SiR.sup.d)--, --P(R.sup.d)--, --P(O)(R.sup.d)--,
--C.dbd.C(R.sup.c)(R.sup.c)-- and --P(OR.sup.d)--, R.sup.a is alkyl
of 1 to 8 carbon atoms R.sup.b is aryl of 6 to 18 carbon atoms
R.sup.c is selected from the group consisting of hydrogen, alkyl of
1 to 8 carbon atoms, aryl of 6 to 18 carbon atoms, alkoxy of 1 to 8
carbon atoms, aryloxy of 6 to 18 carbon atoms, R.sup.a(O)-- or
R.sup.b(O)--; and Rd is one of R.sup.a or R.sup.b; Y is oxygen or
sulfur; and R5s are individually aryl of 6 to 18 carbon-atoms or
alkyl of 1 to 8 carbon atoms.
3. The ligand of claim 1 wherein E is selected from the group
consisting of 15wherein R.sup.6 is alkyl of 1 to 6 carbon atoms or
aryl of 6 to 18 carbon atoms, Z is oxygen or nitrogen and n is an
integer from 2 to 6.
4. A process for the preparation of a linear aldehyde comprising
hydroformylating an internal olefin of 4 to 12 carbon atoms with
carbon monoxide and hydrogen in the presence of a bidentate
phosphine ligand of claim 1.
5. The process of claim 4 wherein E is selected from the group
consisting of 16wherein X is selected from the group consisting of
--O--, --S--, --Si(R.sup.a).sub.2--, --Si(OR.sup.a).sub.2--,
--N(C(O)R.sup.b)--, --N(R.sup.b)--, --C(R.sup.c)(R.sup.c)--,
--C(O)--, --N(SiR.sup.d)--, --P(R.sup.d)--, --P(O)(R.sup.d)--,
--C.dbd.C(R.sup.c)(R.sup.c)-- and --P(OR.sup.d)--, R.sup.a is alkyl
of 1 to 8 carbon atoms R.sup.b is aryl of 6 to 18 carbon atoms
R.sup.c is selected from the group consisting of hydrogen, alkyl of
1 to 8 carbon atoms, aryl of 6 to 18 carbon atoms, alkoxy of 1 to 8
carbon atoms, aryloxy of 6 to 18 carbon atoms, R.sup.a(O)-- or
R.sup.b(O)--; and R.sup.d is one of R.sup.a or R.sup.b; Y is oxygen
or sulfur; and R5s are individually aryl of 6 to 18 carbon atoms or
alkyl of 1 to 8 carbon atoms.
6. The process of claim 4 wherein E is selected from the group
consisting of 17wherein R.sup.6 is alkyl of 1 to 6 carbon atoms or
aryl of 6 to 18 carbon atoms, Z is oxygen or nitrogen and n is an
integer from 2 to 6.
7. The process of claim 4 wherein the reaction is carried out in
the presence of 1 to 1000 .mu.m of rhodium based on the total
reaction mixture.
8. The process of claim 7 wherein rhodium is present at 10 to 250
ppm.
9. The process of claim 7 wherein the ratio of rhodium to ligand is
1:1 to 1:100.
10. The process of claim 7 wherein the ratio of rhodium to ligand
is 1:1 to 1:20.
11. The process of claim 4 wherein the hydroformylation is effected
at 10 to 180.degree. C.
12. The process of claim 4 wherein the hydroformylation is effected
at 80 to 140.degree. C.
13. The process of claim 4 wherein the reaction is effected at a
pressure of 0.1 to 200 bar.
14. The process of claim 4 wherein the hydroformylation is effected
in the presence of a solvent selected from the group consisting of
ether, carbon dioxide, fluorinated hydrocarbons, toluene and
benzene.
15. The process of claim 4 wherein the hydroformylation is effected
in a polar aprotic solvent selected from the group consisting of
dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
16. The process of claim 4 wherein the hydroformylation is effected
in the presence of an oligomeric aldehyde.
17. The process of claim 16 wherein the oligomeric aldehyde is the
trimer of the aldehyde to be formed.
18. The process of claim 11 wherein the hydroformylation is
effected in a two phase with water.
19. The process of claim 4 wherein the ratio of carbon monoxide to
hydrogen is 1:10 to 10:1.
20. The process of claim 4 wherein the ratio of carbon monoxide to
hydrogen is 1:2 to 2:1.
Description
SUMMARY OF THE INVENTION
[0001] Novel bidentate phosphine ligands and a process for
preparing linear aldehydes by hydroformylating internal olefins
using said phosphine ligands.
STATE OF THE ART
[0002] Linear aldehydes, particularly butyraldehyde, are of great
industrial importance and, after further processing to the
alcohols, are widely used in the plasticizer, solvent and polymer
sector. Since mixtures of internal olefins, such as raffinate II,
are produced in large amounts as a by-product in refining and
cracking in the oil-processing industry, hydroformylating internal
olefins to produce linear aldehydes is of great industrial
interest.
[0003] The term "internal olefins" means those olefins which have
at least one non-terminal double bond. However, this does not mean
that internal olefins may not have a terminal double bond.
Therefore, the term "internal olefin" is also taken to mean, for
example, a compound such as 1,3-pentadiene.
[0004] It is known to prepare aldehydes by hydroformylating olefins
using a catalyst with linear and branched aldehydes generally being
formed simultaneously: 2
[0005] For a reaction of this type, bidentate ligands are also used
as a catalyst component. In this case, for example, the ligand can
be used together with a metal or in the form of a complex with a
metal.
[0006] The term "bidentate ligand" means here and hereinafter
molecules of the formula
R.dbd.P-E-P.dbd.R
[0007] wherein, --P.dbd.R and R.dbd.P-- are individually organic
cyclic groups in which the phosphorous atoms are part of the cyclic
system and are linked to the cyclic system via a phosphorus-carbon
bond or a phosphorus-oxygen bond; and E is a bridging group which
links the corresponding phosphorus atoms of the two organic cyclic
groups.
[0008] For industrial hydroformylation reactions, a high
selectivity for the linear or branched aldehydes is particularly
necessary. This selectivity is generally expressed by what is
termed the l/b ratio=(linear aldehyde).multidot.(branched
aldehyde).sup.-1. The hydroformylation is described by Frohning and
Kohlpaintner in Applied Homogeneous Catalysis with organometallic
Compounds, Ed. B. Cornils, W. A. Hermann; V C H, Weinheim 1966,
Vol. 1, pp. 29-104. Another example of the use of bidentate ligands
in catalytic reactions is the hydrogenation described by Brunner in
Applied Homogeneous Catalysis with Organometallic Compounds, Ed. B.
Cornils, W. A. Hermann; V C H, Weinheim 1966, Vol. 1, pp.
201-219.
[0009] EP-0 530 015 A1 describes the use of ligands of the type
R.dbd.P-E-P.dbd.R, such as the ligand of the formula 3
[0010] which are used in metal catalysts for the chiral synthesis
of pharmaceuticals and novel intermediates. JP 07082281 A2 (JP
93-225998) discloses that ligands of this structural type can be
used in hydroformylation for the synthesis of branched olefins with
high selectivity.
[0011] Hopps describes in J. Organ. Chem., 1981, Vol 46, pp.
4422-4427, the use of a ligand of the type R.dbd.P-E-P.dbd.R, such
as the ligand of the formula 4
[0012] for the asymmetric hydroformylation of vinyl acetate, vinyl
propionate and vinyl benzoate, the selectivity for the branched
aldehydes being 75-95%.
[0013] EP-0 213 639 B1 describes a bidentate phosphite ligand of
the type R.dbd.P-E-P.dbd.R, where P.dbd.R or R.dbd.P are
individually organic cyclic groups in which the phosphorus atoms
are part of the cyclic system and are linked to the cyclic system
via a phosphorus-oxygen bond, and E is a bridging group which links
the two phosphorus atoms of the two organic cyclic groups and where
the phosphorus atom is linked to the bridging group E via a
phosphorus-oxygen bond. These ligands are, for example, a ligand of
the formula 5
[0014] and can be used for hydroformylating internal olefins to
produce linear aldehydes. The multistage synthesis of this ligand
and the lower stability of phosphite ligands compared with
phosphine ligands in general is, however, a disadvantage for
industrial implementation.
OBJECTS OF THE INVENTION
[0015] It is an object of the invention to provide novel ligands
and a process for hydroformylating internal olefins to produce
linear aldehydes, which overcomes the disadvantages of the
processes described for hydroformylating internal olefins and which
converts internal olefins to produce linear aldehydes with high
selectivity.
[0016] These and other objects of the invention will become obvious
from the following detailed description.
THE INVENTION
[0017] The novel ligands of the invention are bidentate phosphine
ligands of the formula 6
[0018] wherein R1, R2, R3 and R4 are independently selected from
the group consisting of hydrogen, fluorine, alkyl of 1 to 8 carbon
atoms, alkoxy of 1 to 8 carbon atoms, acyloxy of an organic
carboxylic acid of 1 to 8 carbon atoms, aryl of 6 to 18 carbon
atoms, aryloxy of 6 to 18 carbon atoms, --CN, --CF.sub.3, --CHO,
--SO.sub.3H, --SO3M, --SOR, --SOR, --NH.sub.2. --NH-alkyl of 1 to 8
carbon atoms, --N-alkyl.sub.2 of 1 to 8 carbon atoms, --NHCO-alkyl,
--N-(alkyl)-(CO-(alkyl) where the alkyl have 1 to 4 carbon atoms,
--COO-alkyl of 1 to 8 carbon atoms, --CONH.sub.2, --CO-alkyl of 1
to 8 carbon atoms, --NHCOH, --NHCOO-alkyl of 1 to 4 carbon atoms,
--CO-aryl of 1 to 8 carbon atoms, --COO-aryl of 1 to 8 carbon
atoms, --CHCH--CO.sub.2-alkyl of 1 to 8 carbon atoms,
--PO-(-aryl).sub.2 of 1 to 8 carbon atoms, --PO-(alkyl.sub.2) of 1
to 4 carbon atoms; M is a cation selected from the group consisting
of alkali metal ions, alkaline earth metal ions, --NR.sub.2H.sub.2,
--NR.sub.3H, --NRH.sub.3, --NR.sub.4, --NH.sub.4,
--PR.sub.2H.sub.2, --PR.sub.3H, --PRH.sub.3, --PR.sub.4 and
--PH.sub.4; or R1, R2, R3 and R4, with one another, together form
at least one aliphatic or aromatic ring of 5 to 20 carbon atoms; E
is a bridge linking the two phosphorus atoms, where the number of
atoms situated between the two phosphorus atoms is 2 and 6,
selected from the group consisting of C, N, Si, S, O, P, Fe and As;
X is selected from the group consisting of --O--, --S--,
--Si(R.sup.a).sub.2--, --Si(OR.sup.a).sub.2--, --N(C(O)R.sup.b)--,
--N(R.sup.b)--, --C(R.sup.c)(R.sup.c)--, --C(O)--,
--N(SiRd.sup.4)--, --P(R.sup.d)--, --P(O)(R.sup.d)--,
--C.dbd.C(R.sup.c)(R.sup.c)-- and --P(OR.sup.d)-- wherein
[0019] R.sup.a is alkyl of 1 to 8 carbon atoms,
[0020] R.sup.b is aryl of 6 to 18 carbon atoms,
[0021] R.sup.c is selected from the group consisting of hydrogen,
alkyl of 1 to 8 carbon atoms, aryl of 6 to 18 carbon atoms, alkoxy
of 1 to 8 carbon atoms, aryloxy of 6 to 18 carbon atoms,
R.sup.a(O)-- and R.sup.b(O); and
[0022] R.sup.d is one of R.sup.a or R.sup.b.
[0023] According to a preferred embodiment, E is one of the
following groups: 7
[0024] wherein X is selected from the group consisting of --O--,
--S--, --Si(R.sup.a).sub.2--, --Si(OR.sup.a).sub.2--, --N(C(O)R)--,
--N(R.sup.b)--, --C(R.sup.c)--, --(R.sup.c)--, --C(O)--,
--N(SiR.sup.d)--, --P(R.sup.d)--, --P(O)(R.sup.d)--,
--C.dbd.C(R.sup.c)(R.sup.c)-- and --P(R.sup.d)--,
[0025] R.sup.a is alkyl of 1 to 8 carbon atoms
[0026] R.sup.b is aryl of 6 to 18 carbon atoms
[0027] R.sup.c is selected from the group consisting of hydrogen,
alkyl of 1 to 8 carbon atoms, aryl of 6 to 18 carbon atoms, alkoxy
of 1 to 8 carbon atoms, aryloxy of 6 to 18 carbon atoms,
R.sup.a(O)-- or R.sup.b(O)--;
[0028] and R.sup.d is one of R.sup.a or R.sup.b;
[0029] Y is oxygen or sulfur; and
[0030] R5s are individually aryl of 6 to 18 carbon atoms or alkyl
of 1 to 8 carbon atoms.
[0031] In accordance with a further preferred embodiment of the
invention, E is one of the following groups: 8
[0032] where R6 is alkyl of 1 to 8 carbon atoms or aryl of 6 to 18
carbon atoms; Z is oxygen or nitrogen, and n is an integer of 2 to
6.
[0033] The phosphine ligands of the invention are used, in
particular, in a process for preparing linear aldehydes by
hydroformylating internal olefins of 4 to 12 carbon atoms in the
presence of a bidentate phosphine ligand of the formula 9
[0034] wherein R1, R2, R3, R4, M, E and X are defined as above.
[0035] According to a preferred embodiment of the process of the
invention, E is one of the following groups: 10
[0036] wherein X, Y, R.sup.1 and R.sup.6 are defined as above.
[0037] In accordance with a further preferred embodiment of the
process, E is one of the following groups: 11
[0038] where R.sup.6 is an alkyl of 1 to 8 carbon atoms or aryl of
6 to 18 carbon atoms; Z is oxygen or nitrogen; and n is an integer
of 2 to 6.
[0039] It has proved to be particularly expedient if the reaction
is carried out in the presence of rhodium at a concentration of
from 1 to-1000 ppm, preferably from 10 to 250 ppm, based on the
total reaction mixture. The ratio of rhodium to ligand can, in this
case, be between 1:1, and 1:100, preferably between 1:1 and
1:20.
[0040] The temperature during the reaction is generally between 10
and 180.degree. C., preferably between 80 and 140.degree. C., and
the pressure is between 0.1 and 200 bar, preferably between 1 and
100 bar.
[0041] The reaction can be carried out in the presence of a solvent
which may be selected from the group consisting of ether, Co.sub.2,
fluorinated hydrocarbons, toluene and benzene. However, the solvent
can also be a polar aprotic solvent which is preferably selected
from the group consisting of DMAC, DMF or NMP.
[0042] It is also possible to carry out the reaction in the
presence of an oligomeric linear aldehyde, preferably particular in
the presence of the trimer of the linear aldehyde to be prepared,
which here also acts as solvent. Also, it has proved to be
expedient to carry out the reaction in a two-phase mixture of the
solvent and water.
[0043] The CO/H.sub.2 ratio during the hydroformylation of the
invention is usually between 1:10 and 10:1, preferably between 1:2
and 2:1.
[0044] In the following examples, there are described preferred
embodiments to illustrate the invention. However, it should be
understood that the invention is not intended to be limited to the
specific embodiments.
EXAMPLES
[0045] General Synthesis Method:
[0046] All experiments are carried out using standard Schlenk
techniques under an argon atmosphere. The chemical were obtained
from Acros Chimica and Aldrich Chemical Company.
Rh(CO).sub.2(dipivaloyl methanoate) was prepared by the processes
described in the literature (H. T. Teunissen, F. Bickelhaupt
"Phosphor, Sulfur" 1996 118, pp. 309-312; H. K. A. C. Coolen, P. W.
N. M. van Leeuwen, R. J. M. Nolte "J. Org. Chem." 1966, 61, pp.
4739-4747). The NMR measurements were carried out using a Bruker
AMX 300 spectrometer.
[0047] Preparation of the diphosphine ligands 2a-2c: 12
[0048] 3.7 ml of a solution of N-butyllithium in hexane (2.5 mol,
9.3 mmol) were added to a mixture of 2.00 g of
4,5-dibromo-2,7-di-t-butyl-9,9- -dimethylxanthene (compound 3)
(4.16 mmol) in 50 ml of THF at -60.degree. C. After the resultant
white suspension had been stirred for 2 hours, 2.2 equivalents of
chlorophosphine in 25 ml of toluene were added. The reaction
mixture was slowly heated to ambient temperature and was stirred
overnight. The solvent was removed under vacuum and the residue was
dissolved in a mixture of toluene and saturated sodium chloride
solution in a ratio of 2:1. The organic phase was removed and the
aqueous phase was extracted three times with toluene. After the
combined organic extracts had been dried under vacuum and the
resultant residue haa been washed with hexane, a white powder was
isolated. The ligands were obtained in pure form after
recrystallization; 2a from ethanol (yield 64%), 2b from DCM (yield
52%) and 2c from toluene (yield 75%).
[0049] The physical parameters of the resultant compounds are
reproduced below:
[0050] Properties of 2a:
[0051] mp.: 194-195.degree. C.
[0052] .sup.1H-NMR (in CDCl.sub.3):
[0053] .delta.[ppm]=7.38 (d, .sup.4J(H,H)=2.2 Hz, 2H; H.sup.1.8),
7.24 (m, 20H; phenyl), 6.53 (bd, .sup.4J(H,H)=2.1 Hz, 2H;
H.sup.3.6), 1.68 (s, 6H; CH.sub.3), 1.11 (s, 18H; t=butyl)
[0054] .sup.13C{H}-NMR (in CDCl.sub.3):
[0055] .epsilon.[ppm]=150.7 (t, J(P,C) 19.1 Hz; CO), through-space
P-P coupling=25.2 Hz, 145.4 (C.sup.2.7), 137.0 (t, J(P,C)=13.1 Hz;
PC), 134.2 (t, J(P,C)=20.4 Hz; PCCH); 129.7 (C.sup.3.6) 129.1
(CC.sup.9), 128.3 (d, J(P,C)=6.0 Hz; PCCHCH), 128.3 (PCCHCHCH),
124.9 (t, J(P,C)=18.9 Hz; C.sup.4.5, 123.2 (C.sup.1.8), 35.1
(C.sup.9), 34.7 (C(CH.sub.3).sub.3, 32.4 (C.sup.9CH.sub.3), 31.5
(C(CH.sub.3).sub.3).
[0056] .sup.3P{.sup.1H]-NMR (in CDCl.sub.3):
[0057] .epsilon.[ppm]=-16.2
[0058] Elemental analysis: Calculated: C 81.78% H 6.69%
[0059] Found: 81.71% 7.01%
[0060] Properties of 2b:
[0061] mp.: 330.degree.
[0062] .sup.1H-NMR (in CDCl.sub.3):
[0063] .delta.[ppm]=8.35 (dd, .sup.3J(H,H)=7.5 Hz, .sup.4J(H,H)=1.6
Hz, 4H; DBP-H.sup.1), 7.97 (d, .sup.3J(H,H)=7.5 Hz, 4H; DBP-H4),
7.49 (dt, .sup.3J(H,H)=7.5 Hz, .sup.4J(H,H)=1.4 Hz, 4H;
DBP-H.sup.2), 7.41 (dt, .sup.3J(H,H)=7.4HZ .sup.4J(H,H)=1.3 Hz, 4H;
DBP-H.sup.3), 7.38 (d, .sup.4J(H,H)=2.4 Hz, 2H; H.sup.1.8), 6.76
(dt, .sup.4J(H,H)=2.3 Hz, J(P,H)=2.5 Hz, 2H; H.sup.3.6),
through-space P-P coupling=37.8 Hz, 1.69 (s, 6H; CH.sub.3), 1.12
(s, 18H; t-butyl).
[0064] .sup.13C{.sup.H-NMR (in CDCl.sub.3):
[0065] .delta.[ppm]=151.0 (t, J(P,C)=19.6 Hz; CO), 146 (C27), 144.1
(PCC), 142.5 (t, J(P,C)=4.5 Hz; P,C), 131.9 (t, J(P.C)=26.4 Hz;
DBP-C.sup.4); 12 9.5 (CC.sup.9), 128.7 (DBP-C.sup.2), 127.5 (t,
J(P,C)=3.0 Hz; DBP-C3), 126.5 (C.sup.3.6), 124.5 (C.sup.1.8), 124.5
(m, J(P,C)=25.7 Hz; C.sup.4.5), 121.6 (DBP-C.sup.1), 35.1
(C.sup.9), 34.9 (C(CH.sub.3).sub.3), 33.2 (C.sup.9CH.sub.3), 31.6
(C(CH.sub.3).sub.3).
[0066] .sup.31P{.sup.1H-NMR (in CDCl.sub.3):
[0067] .delta.[ppm]=-20.8
[0068] Elemental analysis: Calculated: C 81.54%, H 5.73%
[0069] Found: 82.19% 6.40%
[0070] Properties of 2c:
[0071] mp.: 336-338.degree. C.
[0072] .sup.1H-NMR (in CDCl.sub.3:
[0073] .delta.[ppm]=8.18 (t, .sup.3J(H,H)=7.2 Hz, .sup.3J(?,H)=14.4
Hz, 4H; PP-H.sup.1), through-space P-P coupling =65 Hz, 7.40 (dt,
.sup.3J(H,H)=7.7 Hz, .sup.4J(H,H)=1.3 Hz, 4H; PP-H.sup.3, 7.26 (s,
2H; H.sup.1.8), 7.24 (d, .sup.3J(H,H)=8.2 Hz, 4H; PP-H.sup.4), 7.17
(t, .sup.3J(H,H)=7.3 Hz, 4H; PP-H.sup.2), 6.67 (s, 2H; H.sup.3.6),
1.55 (s, 6H; CH.sub.3) 1.10 (s, 18H; t-butyl).
[0074] .sup.13C{.sup.1H}-NMR (CDCl.sub.3):
[0075] .delta.[ppm]=155.8 (PP-CO), 149.6 (t, J(P ,C)=21.3 Hz; CO),
145.1 (C.sup.2.7), 135.5 (t, J(P,C)=43.1 Hz; PP-C.sup.1), 130.5
(PP-C.sup.3), 128.8 (CC.sup.9), 123.5 (C.sup.3.6), 125.7 (t,
J(P,C)=29.0 Hz; PP-PC), 123.8 (C.sup.4.5), 123.3 (t, J(P,C)=11.1
Hz; PP-C.sup.2) 118.3 (C.sup.4.5), 117.4 (PP-C.sup.4), 34.4
(C.sup.9), 34.1 (C(CH.sub.3).sub.3), 32.7 (C.sup.9CH.sub.3), 30.9
(C(CH.sub.3).sub.3.
[0076] .sup.31P{.sup.1H}-NM (CDCl.sub.3):
[0077] .delta.[ppm]=-69.9
[0078] Elemental analysis: Calculated: C 78.4-7%, H 5.6%
[0079] Found: 78.53% 6.17%
[0080] The diphosphine ligands 2a, 2b and 2c described above were
used in the hydroformylation of internal olefins in accordance with
the conditions described below:
[0081] The reactions were carried out in a 180 ml stainless steel
autoclave in toluene at 80.degree. C. under a CO/H.sub.2 atmosphere
(ratio 1:1) at an initial pressure of 20 bar. The catalyst
precursor was Rh(CO.sub.2) (dipivaloyl methanoate), the rhodium
concentration was 1.0 mmol, and the ratio of Rh:P:1-octene was
1:10:673. The conversion, the l/b ratio and the selectivities for
the isomerized olefins and the linear aldehyde were determined by
gas chromatography, using decane as internal standard.
[0082] TOF here denotes the turnover frequency which is calculated
as (moles of aldehyde) (moles of catalyst).sup.-1 (h).sup.-1.
1TABLE 1 Results of hydroformylation of 1-octene: Selectivity
Conver- Selectivity (lin. t sion (isomers in aldehyde Ligand (min)
(%) %) l/b in %) TOF PPh.sub.3 5.3 26 1.2 3.1 74 1880 2a 30 21 3.9
49 94 250 2b 24 28 16 65 83 360 2c 8.5 27 13 68 86 1100
[0083]
2TABLE 2 Selectivity Con- (lin. t version aldehyde Ligand Substrate
(h) (%) l/b in %) TOF 2b 2-octene 1.0 10 9.5 90 65 2c 2-octene 1.0
22 9.2 90 112 2b 4-octene 17 54 6.1 86 15 2c 4-octene 17 67 4.4 81
20
[0084] The reaction conditions were identical to those of Table 1,
except that the temperature was 120.degree. C. and the pressure was
2 bar.
3TABLE 3 Results of hydroformylation of n-octene mixture: Con-
Selectivity t version (lin. aldehyde) Ligand (h) (%) l/b in %) TOF
PPh.sub.3 2.8 57 0.5 33 318 2c 2.8 63 1.8 64 393 2c.sup.a 2.0 66
1.4 58 517 2c 1.7 68 1.7 63 648 .sup.aPressure 20 bar.
[0085] The reaction conditions were identical to those of Table 2
except that the pressure was 10 bar.
4TABLE 4 Results of hydroformylation of n-butene mixture: Con-
Selectivity t version (lin. aldehyde Ligand (h) (%) l/b in %) TOF
2c 1,5 82 6,7 87 985 2c.sup.a 1,5 84 4,6 82 1050 .sup.aPressure 20
bar.
[0086] The reaction conditions were identical to those of Table 2
except that the pressure was 10 bar.
[0087] Various modifications of the products and process of the
invention may be made without departing from the spirit or scope
thereof and it is to be understood that the invention is to be
limited only as defined in the appended claims.
* * * * *