U.S. patent application number 14/716521 was filed with the patent office on 2015-11-26 for novel monophosphite ligands having a carbonate group.
This patent application is currently assigned to EVONIK INDUSTRIES AG. The applicant listed for this patent is Katrin Marie DYBALLA, Robert FRANKE. Invention is credited to Katrin Marie DYBALLA, Robert FRANKE.
Application Number | 20150336987 14/716521 |
Document ID | / |
Family ID | 53188858 |
Filed Date | 2015-11-26 |
United States Patent
Application |
20150336987 |
Kind Code |
A1 |
DYBALLA; Katrin Marie ; et
al. |
November 26, 2015 |
NOVEL MONOPHOSPHITE LIGANDS HAVING A CARBONATE GROUP
Abstract
A monophosphite ligand having a carbonate group is useful for
hydroformylation.
Inventors: |
DYBALLA; Katrin Marie;
(Recklinghausen, DE) ; FRANKE; Robert; (Marl,
DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DYBALLA; Katrin Marie
FRANKE; Robert |
Recklinghausen
Marl |
|
DE
DE |
|
|
Assignee: |
EVONIK INDUSTRIES AG
Essen
DE
|
Family ID: |
53188858 |
Appl. No.: |
14/716521 |
Filed: |
May 19, 2015 |
Current U.S.
Class: |
558/271 |
Current CPC
Class: |
B01J 2231/321 20130101;
C07F 9/145 20130101; C07F 9/65744 20130101; B01J 2540/12 20130101;
C07F 9/06 20130101; B01J 31/185 20130101; B01J 2540/10 20130101;
B01J 2531/822 20130101; C07C 45/50 20130101; C07C 47/02 20130101;
C07F 9/65742 20130101; C07C 45/50 20130101 |
International
Class: |
C07F 9/06 20060101
C07F009/06 |
Foreign Application Data
Date |
Code |
Application Number |
May 20, 2014 |
DE |
102014209534.4 |
Claims
1. A compound having one of the two structures I and II:
##STR00026## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7, R.sup.8 are each independently selected from:
--H, --(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.6-C.sub.20)-aryl, --(C.sub.6-C.sub.20)-aryl, halogen,
COO--(C.sub.1-C.sub.12)-alkyl, CONH--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2,
--CO--(C.sub.1-C.sub.12)-alkyl, --CO--(C.sub.6-C.sub.20)-aryl,
--COOH, --OH, --SO.sub.3H, --SO.sub.3Na, --NO.sub.2, --CN,
--NH.sub.2, --N[(C.sub.1-C.sub.12)-alkyl].sub.2; X and Y are each
independently selected from: --(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl-COO--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-CONH--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2,
--(C.sub.4-C.sub.20)-heteroaryl,
--(C.sub.4-C.sub.20-heteroaryl-(C.sub.1-C.sub.12)-alkyl,
--(C.sub.5-C.sub.8)-cycloalkyl-(C.sub.4-C.sub.20)-aryl-CO--(C.sub.6-C.sub-
.20)-aryl, Z is selected from: --(C.sub.1-C.sub.12)-alkyl-,
--(C.sub.6-C.sub.20)-aryl-,
--(C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl-,
--(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl-,
--(C.sub.4-C.sub.20)-heteroaryl-,
--(C.sub.6-C.sub.20)-aryl-CO--(C.sub.6-C.sub.20)-aryl-,
--(C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl-; Q is selected
from: --(C.sub.1-C.sub.18)-alkyl,
--(C.sub.1-C.sub.12)-alkyl-(C.sub.1-C.sub.20)-aryl-,
--(C.sub.1-C.sub.18)-haloalkyl-, --NH--(C.sub.1-C.sub.18)-alkyl,
and wherein the alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl,
aryl and heteroaryl groups mentioned are optionally
substituted.
2. The compound according to claim 1, wherein X and Y are each
independently selected from: --(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-COO--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-CONH--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2,
--(C.sub.4-C.sub.20)-heteroaryl,
--(C.sub.4-C.sub.20)-heteroaryl-(C.sub.1-C.sub.12)-alkyl.
3. The compound according to claim 1, wherein Z is selected from:
--(C.sub.1-C.sub.12)-alkyl-, --(C.sub.6-C.sub.20)-aryl-,
--(C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl-,
--(C.sub.6-C.sub.20)-aryl-CO--(C.sub.6-C.sub.20)-aryl-,
--(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl-,
--(C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl-.
4. The compound according to claim 1, wherein Q is selected from:
--(C.sub.1-C.sub.12)-alkyl-,
--(C.sub.1-C.sub.3)-alkyl-(C.sub.1-C.sub.6)-aryl-,
--(C.sub.1-C.sub.18)-haloalkyl-, --NH--(C.sub.1-C.sub.8)-alkyl.
5. The compound according to claim 1, wherein R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 are each
independently selected from: --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl, --COO--(C.sub.1-C.sub.12)-alkyl,
--CONH--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2,
--CO--(C.sub.1-C.sub.12)-alkyl, --CO--(C.sub.6-C.sub.20)-aryl,
--COOH, --OH, --NH.sub.2, --N[(C.sub.1-C.sub.12)-alkyl].sub.2.
6. The compound according to claim 1, wherein X and Y are the same
radicals.
7. The compound according to claim 1, wherein R.sup.3 and R.sup.6
are each --O--(C.sub.1-C.sub.12)-alkyl.
8. The compound according to claim 1, wherein R.sup.3 and R.sup.6
are each --OMe.
9. The compound according to claim 1, wherein R.sup.1 and R.sup.8
are each --(C.sub.1-C.sub.12)-alkyl.
10. The compound according to claim 1, wherein R.sup.1 and R.sup.8
are each tert-butyl.
11. The compound according to claim 1, having the general structure
III: ##STR00027## wherein R.sup.9, R.sup.10, R.sup.11, R.sup.12,
R.sup.13, R.sup.14, R.sup.15, R.sup.16 are each independently
selected from: --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl, -halogen,
--COO--(C.sub.1-C.sub.12)-alkyl, --CONH--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2,
--CO--(C.sub.1-C.sub.12)-alkyl, --CO--(C.sub.6-C.sub.20)-aryl,
--COOH, --OH, --SO.sub.3H, --SO.sub.3Na, --NO.sub.2, --CN,
--NH.sub.2, --N[(C.sub.1-C.sub.12)-alkyl].sub.2.
12. The compound according to claim 1, having the structure IV:
##STR00028## wherein R.sup.9, R.sup.10, R.sup.11, R.sup.12,
R.sup.13, R.sup.14, R.sup.15, R.sup.16 are each independently
selected from: --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl, -halogen,
--COO--(C.sub.1-C.sub.12)-alkyl, --CONH--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2,
--CO--(C.sub.1-C.sub.12)-alkyl, --CO--(C.sub.6-C.sub.20)-aryl,
--COOH, --OH, --SO.sub.3H, --SO.sub.3Na, --NO.sub.2, --CN,
--NH.sub.2, --N[(C.sub.1-C.sub.12)-alkyl].sub.2.
13. The compound according to claim 1, which is selected from the
group consisting of compounds 1-6: ##STR00029## ##STR00030##
14. The compound according to claim 1, which is one of the
following compounds: ##STR00031## ##STR00032## ##STR00033##
15. A complex, comprising: a compound according to claim 1, and a
metal atom selected from the group consisting of Rh, Ru, Co, Ir and
mixtures thereof.
16. A hydroformylation reaction, comprising: hydroformylating a
compound in the presence of a compound according to claim 1 as a
catalyst.
17. A process, comprising: a) initially charging an olefin; b)
adding i) a complex according to claim 15, or ii) a compound
according to claim 1 and a compound comprising a metal atom
selected from the group consisting of Rh, Ru, Co and Ir, to obtain
a reaction mixture; c) feeding into the reaction mixture H.sub.2
and CO, d) heating the reaction mixture, to obtain conversion of
the olefin to an aldehyde.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The invention relates to novel monophosphite ligands having
a carbonate group, to use thereof as ligands in hydroformylation
and to the hydroformylation process.
[0003] 2. Discussion of the Background
[0004] The reactions between olefin compounds, carbon monoxide and
hydrogen in the presence of a catalyst to give the aldehydes
comprising one additional carbon atom are known as hydroformylation
or oxo synthesis. The catalysts used in these reactions are
frequently compounds of the transition metals of group VIII of the
Periodic Table of the Elements. Known ligands are, for example,
compounds from the classes of the phosphines, phosphites and
phosphonites, each with trivalent phosphorus P.sup.III. A good
overview of the state of the hydroformylation of olefins can be
found in B. CORNILS, W. A. HERRMANN, "Applied Homogeneous Catalysis
with Organometallic Compounds", vol. 1 & 2, VCH, Weinheim,
N.Y., 1996 or R. Franke, D. Selent, A. Borner, "Applied
Hydroformylation", Chem. Rev., 2012, DOI:10.1021/cr3001803.
[0005] Every catalytically active composition has its specific
benefits. According to the feedstock and target product, therefore,
different catalytically active compositions are used.
[0006] The disadvantage of bi- and polydentate phosphine ligands is
a relatively high level of complexity necessary for preparation
thereof. It is therefore often unfeasible to use such systems in
industrial operations. An additional factor is comparatively low
activity, which has to be compensated for by chemical engineering,
through high residence times. This in turn leads to unwanted side
reactions of the products.
[0007] In Angew. Chem. Int. Ed. 2000, 39, No. 9, p. 1639-1641,
Borner et al. describe ligands having one P--C bond and two P--O
bonds; these are thus phosphonites. The phosphonites described
here, when used in hydroformylation, have n/iso selectivities
(n/iso=the ratio of linear aldehyde (=n) to branched (=iso)
aldehyde)) of 0.61 to 1.57.
[0008] The phosphonite ligands described in DE 199 54 721 have a
good n/iso selectivity. However, in-house studies have shown that
the compound II-c (in DE 199 54 721; page 6) has a tendency to
photochemically induced breakdown, and should therefore not be used
on the industrial scale.
[0009] One disadvantage of the ligands having a phosphonite
structure is that their preparation is very complex. However, the
possibility of a favorable and simple synthesis is crucial for the
use of ligands in an industrial scale process.
[0010] Ease of availability and the associated good possibility of
industrial scale use is an important criterion, since the
preparation complexity and the associated production costs for the
ligand may only be so high that the viability of the overall
process in which the ligand is to be used at a later stage is still
assured.
[0011] Rhodium-monophosphite complexes in catalytically active
compositions are suitable for the hydroformylation of branched
olefins having internal double bonds.
[0012] Since the 1970s, there have been descriptions of the use of
"bulky phosphites" in hydroformylation (see, inter alia, van
Leeuwen et al., Journal of Catalysis, 2013, 298, 198-205). These
feature good activity, but the n/i selectivity for terminally
hydroformylated compounds is in need of improvement.
[0013] EP 0 155 508 discloses the use of bisarylene-substituted
monophosphites in the rhodium-catalyzed hydroformylation of
sterically hindered olefins, e.g. isobutene. However, rhodium
concentrations used here are sometimes very high (one being 250
ppm), which is unacceptable for an industrial scale process in view
of the current cost of rhodium and has to be improved.
[0014] For hydroformylation reactions,
tris(2,4-di-tert-butylphenyl)phosphite (TDTBPP) is currently one of
the best-performing monophosphite ligands commercially available,
and is available under the Alkanox 240 trade name (see also R.
Franke, D. Selent, A. Borner, "Applied Hydroformylation", Chem.
Rev., 2012, 112, p. 5681, chapter 3.4.2).
SUMMARY OF THE INVENTION
[0015] The technical object that formed the basis of the present
invention is that of providing a novel monophosphite ligand which
does not have the above-detailed disadvantages from the related art
in the hydroformylation of unsaturated compounds.
[0016] Firstly, the preparation complexity should be lower than for
the above-described phosphonite ligands; secondly, a good n
selectivity should be achieved in relation to the
hydroformylation.
[0017] More particularly, the novel monophosphite ligands should
also be suitable for hydroformylation of industrial olefin mixtures
containing mainly branched olefins having internal double bonds. In
the hydroformylation, at the same time, a high proportion of
desired terminally hydroformylated products should be obtained.
[0018] In addition to aiming for a high reactivity and n/i
selectivity in relation to the unsaturated compounds to be
carbonylated, the stability--specifically the service life--of the
catalytically active composition composed of the metal used in each
case, ligands and further components having an activating effect
with respect to the monophosphite used as ligands is a constant
task in research. This is especially true with regard to
olefin-containing mixtures, specifically in the hydroformylation of
mixtures of linear olefins.
[0019] The above and other objects have been achieved by the
present invention the first embodiment of which includes a compound
having one of the two structures I and II:
##STR00001##
[0020] wherein
[0021] R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6,
R.sup.7, R.sup.8 are each independently selected from: --H,
--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.6-C.sub.20)-aryl, --(C.sub.6-C.sub.20)-aryl, halogen,
COO--(C.sub.1-C.sub.12)-alkyl, CONH--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2,
--CO--(C.sub.1-C.sub.12)-alkyl, --CO--(C.sub.6-C.sub.20)-aryl,
--COOH, --OH, --SO.sub.3H, --SO.sub.3Na, --NO.sub.2, --CN,
--NH.sub.2, --N[C.sub.1-C.sub.12)-alkyl].sub.2;
[0022] X and Y are each independently selected from:
[0023] --(C.sub.1-C.sub.12)-alkyl, --(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl-COO--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-CONH--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2,
--(C.sub.4-C.sub.20)-heteroaryl,
--(C.sub.4-C.sub.20)-heteroaryl-(C.sub.1-C.sub.12)-alkyl,
--(C.sub.5-C.sub.8)-cycloalkyl-(C.sub.4-C.sub.20)-aryl-CO--(C.sub.6-C.sub-
.20)-aryl,
[0024] Z is selected from:
[0025] --(C.sub.1-C.sub.12)-alkyl-, --(C.sub.6-C.sub.20)-aryl-,
--(C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl-,
--(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl-,
--(C.sub.4-C.sub.20)-heteroaryl-,
--(C.sub.6-C.sub.20)-aryl-CO--(C.sub.6-C.sub.20)-aryl-,
--(C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl-;
[0026] Q is selected from:
[0027] --(C.sub.1-C.sub.18)-alkyl-,
--(C.sub.1-C.sub.12)-alkyl-(C.sub.1-C.sub.20)-aryl-,
--(C.sub.1-C.sub.18)-haloalkyl-,
[0028] --NH--(C.sub.1-C.sub.18)-alkyl, and
[0029] wherein the alkyl, heteroalkyl, cycloalkyl,
heterocycloalkyl, aryl and heteroaryl groups mentioned are
optionally substituted.
DETAILED DESCRIPTION OF THE INVENTION
[0030] The present invention relates to a compound having one of
the two general structures I and II:
##STR00002##
[0031] wherein
[0032] R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6,
R.sup.7, R.sup.8 are each independently selected from: --H,
--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.6-C.sub.20)-aryl, --(C.sub.6-C.sub.20)-aryl, halogen
(such as Cl, F, Br, I), COO--(C.sub.1-C.sub.12)-alkyl,
CONH--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2,
--CO--(C.sub.1-C.sub.12)-alkyl, --CO--(C.sub.6-C.sub.20)-aryl,
--COOH, --OH, --SO.sub.3H, --SO.sub.3Na, --NO.sub.2, --CN,
--NH.sub.2, --N[(C.sub.1-C.sub.12)-alkyl].sub.2;
[0033] X and Y are each independently selected from:
[0034] --(C.sub.1-C.sub.12)-alkyl, --(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl-COO--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-CONH--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2,
--(C.sub.4-C.sub.20)-heteroaryl,
--(C.sub.4-C.sub.20)-heteroaryl-(C.sub.1-C.sub.12)-alkyl,
--(C.sub.5-C.sub.8)-cycloalkyl,
--(C.sub.6-C.sub.20)-aryl-CO--(C.sub.6-C.sub.20)-aryl,
[0035] Z is selected from:
[0036] --(C.sub.1-C.sub.12)-alkyl-, --(C.sub.6-C.sub.20)-aryl-,
--(C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl-,
--(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl-,
--(C.sub.4-C.sub.20)-heteroaryl-,
--(C.sub.6-C.sub.20)-aryl-CO--(C.sub.6-C.sub.20)-aryl-,
--(C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl-;
[0037] Q is selected from:
[0038] --(C.sub.1-C.sub.18)-alkyl-,
--(C.sub.1-C.sub.12)-alkyl-(C.sub.1-C.sub.20)-aryl-,
--(C.sub.1-C.sub.18)-haloalkyl-,
[0039] --NH--(C.sub.1-C.sub.18)-alkyl,
[0040] wherein the alkyl, heteroalkyl, cycloalkyl,
heterocycloalkyl, aryl and heteroaryl groups mentioned may be
substituted.
[0041] (C.sub.1-C.sub.12)-Alkyl and O--(C.sub.1-C.sub.12)-alkyl may
each be unsubstituted or substituted by one or more identical or
different radicals selected from (C.sub.3-C.sub.12)-cycloalkyl,
(C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl,
fluorine, chlorine, cyano, formyl, acyl and alkoxycarbonyl.
[0042] (C.sub.3-C.sub.12)-Cycloalkyl and
(C.sub.3-C.sub.12)-heterocycloalkyl may each be unsubstituted or
substituted by one or more identical or different radicals selected
from (C.sub.1-C.sub.12)-alkyl, (C.sub.1-C.sub.12)-alkoxy,
(C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl,
(C.sub.6-C.sub.20)-aryl, fluorine, chlorine, cyano, formyl, acyl
and alkoxycarbonyl.
[0043] (C.sub.6-C.sub.20)-Aryl and
--(C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl-may each be
unsubstituted or substituted by one or more identical or different
radicals selected from:
[0044] --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl, -halogen (such as Cl, F, Br, I),
--COO--(C.sub.1-C.sub.12)-alkyl, --CONH--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2,
--CO--(C.sub.1-C.sub.12)-alkyl, --CO--(C.sub.6-C.sub.20)-aryl,
--COOH, --OH, --SO.sub.3H, --SO.sub.3Na, --NO.sub.2, --CN,
--NH.sub.2, --N[(C.sub.1-C.sub.12)-alkyl].sub.2.
[0045] All ranges described herein include all values and subvalues
between the lower and upper limits of such range.
[0046] In the context of the invention, the expression
--(C.sub.1-C.sub.12)-alkyl encompasses straight-chain and branched
alkyl groups. Preferably, these groups are unsubstituted
straight-chain or branched --(C.sub.1-C.sub.8)-alkyl groups and
most preferably --(C.sub.1-C.sub.6)-alkyl groups. Examples of
(C.sub.1-C.sub.12)-alkyl groups are especially methyl, ethyl,
propyl, isopropyl, n-butyl, isobutyl, 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, 1,1-dimethylbutyl, 1,2-dimethylbutyl,
2,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl,
3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,
1-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl,
2-ethylpentyl, 1-propylbutyl, n-octyl, 2-ethylhexyl,
2-propylheptyl, nonyl, decyl.
[0047] The elucidations relating to the expression
--(C.sub.1-C.sub.12)-alkyl also apply to the alkyl groups in
--O--(C.sub.1-C.sub.12)-alkyl, i.e. in --(C.sub.1-C.sub.12)-alkoxy.
Preferably, these groups are unsubstituted straight-chain or
branched --(C.sub.1-C.sub.6)-alkoxy groups.
[0048] Substituted --(C.sub.1-C.sub.12)-alkyl groups and
substituted --(C.sub.1-C.sub.12)-alkoxy groups may have one or more
substituents, depending on their chain length. The substituents are
preferably each independently selected from
--(C.sub.3-C.sub.12)-cycloalkyl,
--(C.sub.3-C.sub.12)-heterocycloalkyl, --(C.sub.6-C.sub.20)-aryl,
fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl.
[0049] The expression "--(C.sub.3-C.sub.12)-cycloalkyl", in the
context of the present invention, encompasses mono-, bi- or
tricyclic hydrocarbyl radicals having 3 to 12, especially 5 to 12,
carbon atoms. These include cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclopentadecyl,
norbonyl and adamantyl.
[0050] The expression "--(C.sub.3-C.sub.12)-heterocycloalkyl
groups", in the context of the present invention, encompasses
nonaromatic saturated or partly unsaturated cycloaliphatic groups
having 3 to 12, especially 5 to 12, carbon atoms. The
--(C.sub.3-C.sub.12)-heterocycloalkyl groups have preferably 3 to
8, more preferably 5 or 6, ring atoms. In the heterocycloalkyl
groups, as opposed to the cycloalkyl groups, 1, 2, 3 or 4 of the
ring carbon atoms are replaced by heteroatoms or
heteroatom-containing groups. The heteroatoms or the
heteroatom-containing groups are preferably selected from --O--,
--S--, --N--, --N(.dbd.O)--, --C(.dbd.O)-- and --S(.dbd.O)--.
Examples of --(C.sub.3-C.sub.12)-heterocycloalkyl groups are
tetrahydrothiophenyl, tetrahydrofuryl, tetrahydropyranyl and
dioxanyl.
[0051] Substituted --(C.sub.3-C.sub.12)-cycloalkyl groups and
substituted --(C.sub.3-C.sub.12)-heterocycloalkyl groups may have
one or more (e.g. 1, 2, 3, 4 or 5) further substituents, depending
on their ring size. These substituents are preferably each
independently selected from --(C.sub.1-C.sub.12)-alkyl,
--(C.sub.1-C.sub.12)-alkoxy, --(C.sub.3-C.sub.12)-cycloalkyl,
--(C.sub.3-C.sub.12)-heterocycloalkyl, --(C.sub.6-C.sub.20)-aryl,
fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl.
Substituted --(C.sub.3-C.sub.12)-cycloalkyl groups preferably bear
one or more --(C.sub.1-C.sub.6)-alkyl groups. Substituted
--(C.sub.3-C.sub.12)-heterocycloalkyl groups preferably bear one or
more --(C.sub.1-C.sub.6)-alkyl groups.
[0052] In the context of the present invention, the expression
--(C.sub.6-C.sub.20)-aryl and
--(C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl-encompasses mono-
or polycyclic aromatic hydrocarbyl radicals. These have 6 to 20
ring atoms, more preferably 6 to 14 ring atoms, especially 6 to 10
ring atoms. Aryl is preferably --(C.sub.6-C.sub.10)-aryl and
--(C.sub.6-C.sub.10)-aryl-(C.sub.6-C.sub.10)-aryl. Aryl is
especially phenyl, naphthyl, indenyl, fluorenyl, anthracenyl,
phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, coronenyl. More
particularly, aryl is phenyl, naphthyl and anthracenyl.
[0053] Substituted --(C.sub.6-C.sub.20)-aryl groups and
--(C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl groups may have
one or more (e.g. 1, 2, 3, 4 or 5) substituents, depending on their
ring size. These substituents are preferably each independently
selected from --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl, -halogen (such as Cl, F, Br, I),
--COO--(C.sub.1-C.sub.12)-alkyl, --CONH--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2,
--CO--(C.sub.1-C.sub.12)-alkyl, --CO--(C.sub.6-C.sub.20)-aryl,
--COOH, --OH, --SO.sub.3H, --SO.sub.3Na, --NO.sub.2, --CN,
--NH.sub.2, --N[(C.sub.1-C.sub.12)-alkyl].sub.2.
[0054] Substituted --(C.sub.6-C.sub.20)-aryl groups and
--(C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl groups are
preferably substituted --(C.sub.6-C.sub.10)-aryl groups and
--(C.sub.6-C.sub.10)-aryl-(C.sub.6-C.sub.10)-aryl groups,
especially substituted phenyl or substituted naphthyl or
substituted anthracenyl. Substituted-(C.sub.6-C.sub.20)-aryl groups
preferably bear one or more, for example 1, 2, 3, 4 or 5,
substituents selected from --(C.sub.1-C.sub.12)-alkyl groups,
--(C.sub.1-C.sub.12)-alkoxy groups.
[0055] In one embodiment, Q is selected from:
[0056] --(C.sub.1-C.sub.12)-alkyl-,
--(C.sub.1-C.sub.3)-alkyl-(C.sub.1-C.sub.6)-aryl-,
--(C.sub.1-C.sub.18)-haloalkyl-, --NH--(C.sub.1-C.sub.8)-alkyl.
[0057] In one embodiment, Q is selected from:
[0058] --(C.sub.1-C.sub.8)-alkyl-, especially -methyl, -ethyl,
-butyl, -tert-butyl, -2,4-dimethylpent-3-yl and -benzyl,
-2,2,3-trichloroethyl.
[0059] In one embodiment, Q is selected from:
[0060] --(C.sub.1-C.sub.8)-alkyl, wherein Q is not -tert-butyl.
[0061] In one embodiment, Q is not -tert-butyl.
[0062] In one embodiment, X and Y are each independently selected
from:
[0063] --(C.sub.1-C.sub.12)-alkyl, --(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-COO--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-CONH--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2,
--(C.sub.4-C.sub.20)-heteroaryl,
--(C.sub.4-C.sub.20)-heteroaryl-(C.sub.1-C.sub.12)-alkyl.
[0064] In one embodiment, X and Y are each independently selected
from:
[0065] --(C.sub.1-C.sub.12)-alkyl, --(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-COO--(C.sub.1-C.sub.12)-alkyl.
[0066] In one embodiment, X and Y are each independently selected
from:
[0067] --(C.sub.1-C.sub.12)-alkyl, --(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-O--(C.sub.1-C.sub.12)-alkyl.
[0068] In one embodiment, Z is selected from:
[0069] --(C.sub.1-C.sub.12)-alkyl-, --(C.sub.6-C.sub.20)-aryl-,
--(C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl-,
--(C.sub.6-C.sub.20)-aryl-CO--(C.sub.6-C.sub.20)-aryl-,
--(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl-,
--(C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl-.
[0070] In one embodiment, Z is:
##STR00003##
[0071] In one embodiment, Z is:
[0072] --(C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl-.
[0073] In one embodiment, R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6, R.sup.7, R.sup.8 are each independently selected
from:
[0074] --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl, --COO--(C.sub.1-C.sub.12)-alkyl,
--CONH--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2,
--CO--(C.sub.1-C.sub.12)-alkyl, --CO--(C.sub.6-C.sub.20)-aryl,
--COOH, --OH, --NH.sub.2, --N[(C.sub.1-C.sub.12)-alkyl].sub.2.
[0075] In one embodiment, R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6, R.sup.7, R.sup.8 are each independently selected
from:
[0076] --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl, --COO--(C.sub.1-C.sub.12)-alkyl,
--N[(C.sub.1-C.sub.12)-alkyl].sub.2.
[0077] In one embodiment, R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6, R.sup.7, R.sup.8 are each independently selected
from:
[0078] --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, --(C.sub.6-C.sub.20)-aryl.
[0079] In one embodiment, X and Y are the same radicals.
[0080] In one embodiment, R.sup.3 and R.sup.6 are each
--O--(C.sub.1-C.sub.12)-alkyl.
[0081] In one embodiment, R.sup.3 and R.sup.6 are each --OMe.
[0082] In one embodiment, R.sup.1 and R.sup.8 are each
--(C.sub.1-C.sub.12)-alkyl.
[0083] In one embodiment, R.sup.1 and R.sup.8 are each
tert-butyl.
[0084] In one embodiment, R.sup.1, R.sup.3, R.sup.6 and R.sup.8 are
each --(C.sub.1-C.sub.12)-alkyl.
[0085] In one embodiment, R.sup.1, R.sup.3, R.sup.6 and R.sup.8 are
each methyl.
[0086] In one embodiment, R.sup.1, R.sup.3, R.sup.6 and R.sup.8 are
each tert-butyl.
[0087] In one embodiment, R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are each --H.
[0088] In one embodiment, the compound has the general structure
III:
##STR00004##
wherein R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14,
R.sup.15, R.sup.16 are each independently selected from:
[0089] --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl, -halogen (such as Cl, F, Br, I),
--COO--(C.sub.1-C.sub.12)-alkyl, --CONH--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2,
--CO--(C.sub.1-C.sub.12)-alkyl, --CO--(C.sub.6-C.sub.20)-aryl,
--COOH, --OH, --SO.sub.3H, --SO.sub.3Na, --NO.sub.2, --CN,
--NH.sub.2, --N[(C.sub.1-C.sub.12)-alkyl].sub.2.
[0090] In one embodiment, R.sup.9, R.sup.10, R.sup.11, R.sup.12,
R.sup.13, R.sup.14, R.sup.15, R.sup.16 are each independently
selected from:
[0091] --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl, --COO--(C.sub.1-C.sub.12)-alkyl,
--CONH--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2,
--CO--(C.sub.1-C.sub.12)-alkyl, --CO--(C.sub.6-C.sub.20)-aryl,
--COOH, --OH, --NH.sub.2, --N[(C.sub.1-C.sub.12)-alkyl].sub.2.
[0092] In one embodiment, R.sup.9, R.sup.10, R.sup.11, R.sup.12,
R.sup.13, R.sup.14, R.sup.15, R.sup.16 are each independently
selected from:
[0093] --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl, --COO--(C.sub.1-C.sub.12)-alkyl,
--N[(C.sub.1-C.sub.12)-alkyl].sub.2.
[0094] In one embodiment, R.sup.9, R.sup.10, R.sup.11, R.sup.12,
R.sup.13, R.sup.14, R.sup.15, R.sup.16 are each independently
selected from:
[0095] --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, --(C.sub.6-C.sub.20)-aryl,
[0096] where alkyl comprises 1-12 carbon atoms, preferably 1-10
carbon atoms, for example primary, secondary or tertiary alkyl
group such as methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl,
t-butyl, t-butylethyl, t-butylpropyl, n-hexyl, amyl, sec-amyl,
t-amyl, isooctyl, 2-ethylhexyl, decyl, dodecyl and octadecyl
groups.
[0097] In one embodiment, R.sup.11 and R.sup.14 are each
--O--(C.sub.1-C.sub.12)-alkyl.
[0098] In one embodiment, R.sup.11 and R.sup.14 are each --OMe.
[0099] In one embodiment, R.sup.9 and R.sup.16 are each
--(C.sub.1-C.sub.12)-alkyl.
[0100] In one embodiment, R.sup.9 and R.sup.16 are each
tert-butyl.
[0101] In one embodiment, R.sup.9, R.sup.11, R.sup.14 and R.sup.16
are each --(C.sub.1-C.sub.12)-alkyl.
[0102] In one embodiment, R.sup.9, R.sup.10, R.sup.14 and R.sup.16
are each methyl.
[0103] In one embodiment, R.sup.9, R.sup.11, R.sup.14 and R.sup.16
are each tert-butyl.
[0104] In one embodiment, 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 --H.
[0105] In one embodiment, the compound has the general structure
IV:
##STR00005##
where R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14,
R.sup.15, R.sup.16 are each independently selected from:
[0106] --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl, -halogen (such as Cl, F, Br, I),
--COO--(C.sub.1-C.sub.12)-alkyl, --CONH--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2,
--CO--(C.sub.1-C.sub.12)-alkyl, --CO--(C.sub.6-C.sub.20)-aryl,
--COOH, --OH, --SO.sub.3H, --SO.sub.3Na, --NO.sub.2, --CN,
--NH.sub.2, --N[(C.sub.1-C.sub.12)-alkyl].sub.2.
[0107] In one embodiment, R.sup.9, R.sup.10, R.sup.11, R.sup.12,
R.sup.13, R.sup.14, R.sup.15, R.sup.16 are each independently
selected from:
[0108] --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl, --COO--(C.sub.1-C.sub.12)-alkyl,
--CONH--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2,
--CO--(C.sub.1-C.sub.12)-alkyl, --CO--(C.sub.6-C.sub.20)-aryl,
--COOH, --OH, --NH.sub.2, --N[(C.sub.1-C.sub.12)-alkyl].sub.2.
[0109] In one embodiment, R.sup.9, R.sup.10, R.sup.11, R.sup.12,
R.sup.13, R.sup.14, R.sup.15, R.sup.16 are each independently
selected from:
[0110] --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.6-C.sub.20)-aryl,
--(C.sub.6-C.sub.20)-aryl, --COO--(C.sub.1-C.sub.12)-alkyl,
--N[(C.sub.1-C.sub.12)-alkyl].sub.2.
[0111] In one embodiment, R.sup.9, R.sup.10, R.sup.11, R.sup.12,
R.sup.13, R.sup.14, R.sup.15, R.sup.16 are each independently
selected from:
[0112] --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, --(C.sub.6-C.sub.20)-aryl,
[0113] where alkyl comprises 1-12 carbon atoms, preferably 1-10
carbon atoms, for example primary, secondary or tertiary alkyl
group such as methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl,
t-butyl, t-butylethyl, t-butylpropyl, n-hexyl, amyl, sec-amyl,
t-amyl, isooctyl, 2-ethylhexyl, decyl, dodecyl and octadecyl
groups.
[0114] In one embodiment, R.sup.11 and R.sup.14 are each
--O--(C.sub.1-C.sub.12)-alkyl.
[0115] In one embodiment, R.sup.11 and R.sup.14 are each --OMe.
[0116] In one embodiment, R.sup.9 and R.sup.16 are each
--(C.sub.1-C.sub.12)-alkyl.
[0117] In one embodiment, R.sup.9 and R.sup.16 are each
tert-butyl.
[0118] In one embodiment, R.sup.9, R.sup.11, R.sup.14 and R.sup.16
are each --(C.sub.1-C.sub.12)-alkyl.
[0119] In one embodiment, R.sup.9, R.sup.11, R.sup.14 and R.sup.16
are each methyl.
[0120] In one embodiment, R.sup.9, R.sup.11, R.sup.14 and R.sup.16
are each tert-butyl.
[0121] In one embodiment, 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 --H.
[0122] As well as the compounds, also claimed is a complex
comprising these compounds.
[0123] Complex comprising: [0124] an above-described compound,
[0125] a metal atom selected from: Rh, Ru, Co, Ir.
[0126] In a preferred embodiment, the metal is Rh.
[0127] In this regard, see R. Franke, D. Selent, A. Borner,
"Applied Hydroformylation", Chem. Rev., 2012,
DOI:10.1021/cr3001803; p. 5688, Scheme 12 "General Method for the
Preparation of a P-Modified Rh precatalyst" and references cited
therein, and also P. W. N. M. van Leeuwen, in Rhodium Catalyzed
Hydroformylation, P. W. N. M. van Leeuwen, C. Claver (eds.),
Kluwer, Dordrecht, 2000, inter alia p. 48 ff, p. 233 ff. and
references cited therein, and also K. D. Wiese and D. Obst in Top.
Organomet. Chem. 2006, 18, 1-13; Springer Verlag Berlin Heidelberg
2006 p. 6 ff and references cited therein.
[0128] Additionally claimed is the use of the ligand as ligand in a
ligand-metal complex for catalysis of a hydroformylation
reaction.
[0129] Use of an Above-Described Ligand in a Ligand-Metal Complex
for Catalysis of a Hydroformylation Reaction.
[0130] The process in which the ligand is used as ligand in a
ligand-metal complex for conversion of an olefin to an aldehyde is
likewise claimed.
[0131] Process comprising the process steps of:
[0132] a) initially charging an olefin,
[0133] b) adding an above-described complex,
[0134] or an above-described compound and a substance including a
metal atom selected from: Rh, Ru, Co, Ir,
[0135] c) feeding in H.sub.2 and CO,
[0136] d) heating the reaction mixture, with conversion of the
olefin to an aldehyde.
[0137] In this process, process steps a) to d) can be effected in
any desired sequence.
[0138] The reaction is conducted under customary conditions.
[0139] Preference is given to a temperature of 80.degree. C. to
160.degree. C. and a pressure of 1 to 300 bar.
[0140] Particular preference is given to a temperature of
100.degree. C. to 160.degree. C. and a pressure of 15 to 250
bar.
[0141] In a preferred embodiment, the metal is Rh.
[0142] The reactants for the hydroformylation in the process of the
invention are olefins or mixtures of olefins, especially
monoolefins having 2 to 24, preferably 3 to 16 and more preferably
3 to 12 carbon atoms, having terminal or internal C--C double
bonds, for example 1-propene, 1- or 2-pentene, 2-methyl-1-butene,
2-methyl-2-butene, 3-methyl-1-butene, 1-, 2- or 3-hexene, the
C.sub.6 olefin mixture obtained in the dimerization of propene
(dipropene), heptenes, 2- or 3-methyl-1-hexenes, octenes,
2-methylheptenes, 3-methylheptenes, 5-methyl-2-heptene,
6-methyl-2-heptene, 2-ethyl-1-hexene, the C.sub.8 olefin mixture
obtained in the dimerization of butenes (dibutene), nonenes, 2- or
3-methyloctenes, the C.sub.9 olefin mixture obtained in the
trimerization (tripropene), decenes, 2-ethyl-1-octene, dodecenes,
the C.sub.12 olefin mixture obtained in the tetramerization or the
trimerization of butenes (tetrapropene or tributene), tetradecenes,
hexadecenes, the C.sub.16 olefin mixture obtained in the
tetramerization of butenes (tetrabutene), and olefin mixtures
prepared by cooligomerization of olefins having different numbers
of carbon atoms (preferably 2 to 4).
[0143] The process according to the invention using the compounds
according to the invention can be used to hydroformylate
.alpha.-olefins, terminally branched, internal and internally
branched olefins. What is remarkable is the high yield of
terminally hydroformylated olefin, even when only a small
proportion of olefins having a terminal double bond was present in
the reactant.
[0144] The following structures show possible working examples of
the ligand:
##STR00006## ##STR00007##
The invention is to be illustrated in detail hereinafter by working
examples.
[0145] General Operating Procedures
ABBREVIATIONS
[0146] ACN=acetonitrile [0147] EtOAc=ethyl acetate [0148]
acac=acetylacetonate [0149] NEt.sub.3=triethylamine [0150]
DMAP=dimethylaminopyridine [0151] CH.sub.2Cl.sub.2=dichloromethane
[0152] TIPB=1,2,4,5-tetraisopropylbenzene
[0153] All the preparations which follow were carried out under
protective gas using standard Schlenk techniques. The solvents were
dried over suitable desiccants before use (Purification of
Laboratory Chemicals, W. L. F. Armarego (author), Christina Chai
(author), Butterworth Heinemann (Elsevier), 6th edition, Oxford
2009).
[0154] All preparative operations were effected in baked-out
vessels. The products were characterized by means of NMR
spectroscopy. Chemical shifts (.delta.) are reported in ppm. The
.sup.31P NMR signals were referenced according to:
SR.sub.31P=SR.sub.1H*(BF.sub.31P/BF.sub.1H)=SR.sub.1H*0.4048.
(Robin K. Harris, Edwin D. Becker, Sonia M. Cabral de Menezes,
Robin Goodfellow, and Pierre Granger, Pure Appl. Chem., 2001, 73,
1795-1818; Robin K. Harris, Edwin D. Becker, Sonia M. Cabral de
Menezes, Pierre Granger, Roy E. Hoffman and Kurt W. Zilm, Pure
Appl. Chem., 2008, 80, 59-84).
[0155] Nuclear resonance spectra were recorded using Bruker Avance
300 or Bruker Avance 400, gas chromatography analysis was effected
using an Agilent GC 7890A, the elemental analysis was effected
using Leco TruSpec CHNS and Varian ICP-OES 715, and the ESI-TOF
mass spectroscopy using Thermo Electron Finnigan MAT 95-XP and
Agilent 6890 N/5973 instruments.
[0156] A general synthesis route is shown in the following reaction
scheme:
##STR00008##
[0157] The reaction routes shown are merely illustrative and are
shown in highly simplified form. Thus, if required, base can be
used additionally in all the steps. In addition, the bases
specified in the individual synthesis stages may be replaced by
other commercially available bases known to those skilled in the
art.
[0158] Relevant carbonate groups and the preparation thereof (see
also: P. G. M. Wuts, T. W. Greene "Greene's Protective Groups in
Organic Synthesis", fourth edition, 2007, John Wiley and Sons;
Hoboken, N.J.): [0159] methyl (E. Fischer, H. O. L. Fischer, Ber.
46, 1138, (1913)) [0160] ethyl (analogously to E. Fischer, H. O. L.
Fischer, Ber. 46, 1138, (1913)) [0161] tert-butyl (BOC) (see below;
M. M. Hansen, J. R. Riggs; Tetrahedron Lett., 39, 2705 (1998))
[0162] 1-adamantyl (Adoc) (B. Nyasse, U. Ragnarsson, Acta Chem.
Scand., 47, 374 (1993)) [0163] 2,4-dimethylpent-3-yl (DOC) (K.
Rosenthal, A. Karlstrom, A. Unden, Tetrahedron Lett., 38, 1075,
(1997)) [0164] 2,2,3-trichloroethyl (T. B. Windholz, D. B. R.
Johnston, Tetrahedron Lett., 8, 2555, (1967)) [0165] benzyl (M.
Kuhn, A. von Wartburg, Helv. Chim. Acta, 52, 948, (1969)) [0166]
likewise carbamates (ArOCONHR) (G. Jager, R. Geiger, W. Siedel,
Chem. Ber. 101, 2762 (1968))
[0167] Examples of Compounds Having a Carbonate Group:
##STR00009## ##STR00010## ##STR00011##
Synthesis of Ligand 1
Reaction
[0168] scheme:
##STR00012##
Introduction of the BOC Group:
##STR00013##
[0170] In a 21 Schlenk flask, 400 mmol (143.8 g) of
3,3'-di-tert-butyl-5,5'-dimethoxy-[1,1'-biphenyl]-2,2'-diol and 40
mmol (4.8 g) of N,N-dimethylaminopyridine (DMAP) were dissolved in
900 ml of CH.sub.2Cl.sub.2. Subsequently, at room temperature, 400
mmol (88 g) of di-tert-butyl dicarbonate were dissolved in 280 ml
of CH.sub.2Cl.sub.2, transferred to a 500 ml dropping funnel and
added dropwise to the biphenol/DMAP solution at 32.degree. C.
within one hour. The solution was stirred at room temperature
overnight. The next morning, the solvent was removed under reduced
pressure. The slightly waxy, reddish solid was admixed with 800 ml
of n-heptane and stirred overnight. This gave a white residue which
was filtered off, washed twice with 50 ml of n-heptane and then
dried. The target product was obtained as a white solid (161.6 g,
84%). .sup.1H NMR (toluene-d.sub.8): 95% and further
impurities.
Reaction of tert-butyl
(3,3'-di-tert-butyl-2'-hydroxy-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)carbon-
ate with phosphorus trichloride
##STR00014##
[0172] In a 250 ml Schlenk flask which had been repeatedly
evacuated and filled with inert gas, 12 g (0.026 mol) of tert-butyl
(3,3'-di-tert-butyl-2'-hydroxy-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)carbon-
ate were dissolved by stirring in 120 ml of dried toluene and 12.8
ml (0.091 mol) of triethylamine.
[0173] In a second 500 ml Schlenk flask, 100 ml of dried toluene
were first stirred together with 8.1 ml (0.091 mol) of phosphorus
trichloride. Subsequently, the phosphorus trichloride-toluene
solution was added dropwise to the previously prepared
carbonate-amine-toluene solution at room temperature within 30
minutes. On completion of addition, the mixture was heated to
80.degree. C. for 30 minutes and cooled to room temperature
overnight.
[0174] The next morning, the mixture was filtered, the solids were
washed with 50 ml of dried toluene, and the filtrate was
concentrated to dryness. The target product was obtained as a solid
(13.1 g, 89%). .sup.31P NMR (202.4 MHz, toluene-d.sub.8): 203.2 and
203.3 ppm (100%).
Reaction of tert-butyl
(3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy-[1,1'-biph-
enyl]-2-yl)carbonate with
3,3',5,5'-tetramethyl-(1,1'-biphenyl)-2,2'-diol
##STR00015##
[0176] In a 1 l Schlenk flask which had been repeatedly evacuated
and filled with inert gas, 24.7 g (0.044 mol) of tert-butyl
(3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy-[1,1'-biph-
enyl]-2-yl)carbonate were dissolved in 400 ml of acetonitrile.
[0177] In a second Schlenk flask (1 l) which had been repeatedly
evacuated and filled with inert gas, 10.8 g (0.044 mol) of
3,3',5,5'-tetramethyl-(1,1'-biphenyl)-2,2'-diol were dissolved by
stirring in 200 ml of acetonitrile and 13.1 ml (0.011 mol) of dried
triethylamine. Subsequently, the chlorophosphite solution was
slowly added dropwise to the biphenol-triethylamine solution and
the mixture was stirred overnight.
[0178] The mixture was then filtered and the residue was washed
twice with 15 ml of acetonitrile.
[0179] The filtrate was concentrated under reduced pressure until a
solid precipitated out. The latter was filtered and dried. The
target product was obtained as a white solid (28.5 g, 87%).
.sup.31P NMR (202.4 MHz, toluene-d.sub.8): 139.4 ppm (98.5%).
##STR00016##
[0180] Spectrometer: Bruker Avance 500 MHz FT spectrometer
[0181] Solvent: 1,1,2,2-tetrachloroethane (TCE)
[0182] Temperature: 353 K (80.degree. C.)
[0183] Referencing: .sup.1H NMR, .sup.13C NMR: TMS=0 [0184]
.sup.31P NMR:
SR.sub.31P=SR.sub.1H*(BF.sub.31P/BF.sub.1H)=SR.sub.1H*0.404807
TABLE-US-00001 [0184] TABLE 1 Assignment of .sup.1H chemical shifts
of 1 .delta./ppm Intensity Multiplicity Assignment 1.13 9H s 17d
(tert-butyl) 1.20 9H s 20d (O-tert-butyl) 1.35 9H s 17c
(tert-butyl) 2.02 3H broad s 7b (methyl) 2.28 3H s 8b (methyl)
2.31/2.32 6H broad s 7a (methyl)/8a (methyl) 3.75 3H s 15c
(O-methyl) 3.78 3H s 15d (O-methyl) 6.68 1H d 11d 6.83 1H d 11c
6.88 2H (1 + 1) m 5b, 13d 6.94 1H d 13c 6.96 1H s 5a 6.99 2H (1 +
1) s 3a + 3b s: singlet d: doublet t: triplet q: quartet m:
multiplet
TABLE-US-00002 TABLE 2 Assignment of .sup.13C chemical shifts of 1
.delta./ppm Intensity Group Assignment 16.35 1 CH.sub.3 7b 16.61 1
CH.sub.3 7a 20.66 1 CH.sub.3 8b 20.71 1 CH.sub.3 8a 27.38 3
CH.sub.3 20d 30.27 3 CH.sub.3 17d 30.41 3 CH.sub.3 17c 34.85 1
C.sub.q 16c 35.02 1 C.sub.q 16d 55.67 1 CH.sub.3 15d 55.79 1
CH.sub.3 15c 81.67 1 C.sub.q 19d 113.86 1 CH 11c 114.01 1 CH 11d
114.14 1 CH 13c 114.60 1 CH 13d 127.65 1 CH 3b 127.88 1 CH 3a
128.72 1 C.sub.q 10d 130.01 1 C.sub.q 6b 130.77 1 C.sub.q 6a 130.86
1 CH 5b 130.92 1 CH 5a 131.37 1 C.sub.q 2b 131.50 1 C.sub.q 2a
133.49 1 C.sub.q 4b 133.65 1 C.sub.q 4a 135.68 1 C.sub.q 10c 142.09
1 C.sub.q 9d 142.37 1 C.sub.q 14d 143.60 1 C.sub.q 9c 144.05 1
C.sub.q 14c 145.88 1 C.sub.q 1b 146.00 1 C.sub.q 1a 151.27 1
C.sub.q 18d 154.18 1 C.sub.q 12d 157.19 1 C.sub.q 12c
Synthesis of Ligand 2
Reaction of tert-butyl
(3,3'-di-tert-butyl-2'-hydroxy-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)carbon-
ate with 2-chloro-4,4,5,5-tetraphenyl-1,3,2-dioxaphospholane
##STR00017##
[0186] In a 250 ml Schlenk flask which had been repeatedly
evacuated and filled with inert gas, 9.1 g (0.021 mol) of
2-chloro-4,4,5,5-tetraphenyl-1,3,2-dioxaphospholane were dissolved
in 75 ml of dried toluene.
[0187] In a second Schlenk flask (250 ml), 9.2 g (0.02 mol) of
tert-butyl
(3,3'-di-tert-butyl-2'-hydroxy-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)carbon-
ate and 2.3 g (0.02 mol) of potassium tert-butoxide were dissolved
in 75 ml of dried toluene while stirring.
[0188] Subsequently, the carbonate/potassium tert-butoxide/toluene
mixture was slowly added dropwise at room temperature to the
chlorophosphite solution, and the mixture was stirred at room
temperature overnight.
[0189] Thereafter, the solvent was removed under reduced pressure.
The resultant residue was stirred in 75 ml of dried acetonitrile
for 5 hours. The solids were filtered, washed with dried
acetonitrile and dried. The target product was obtained as a white
solid (15.3 g, 90%). .sup.31P NMR (202.4 MHz, toluene-d.sub.8):
147.0 ppm (99%).
##STR00018##
Referencing:
[0190] .sup.1H NMR: TMS=0 ppm, .sup.31P NMR:
SR.sub.31P=SR.sub.1H*(BF.sub.31P/BF.sub.1H)=SR.sub.1H*0.404807
TABLE-US-00003 TABLE 3 Assignment of the .sup.13C chemical shifts
of 2 .delta. [ppm] Intensity Group Assignment 157.31 1 .times. C
C.sub.q C9 155.29 1 .times. C C.sub.q C16 152.22 1 .times. C
C.sub.q C24 143.68 1 .times. C C.sub.q C13 143.66/143.54 2 .times.
C C.sub.q C7, C14 143.35 1 .times. C C.sub.q C6 142.99/142.80 4
.times. C C.sub.q C2 142.72/142.49 135.65 1 .times. C C.sub.q C11
132.78 1 .times. C C.sub.q C12 131.30/130.45 8 .times. C CH C4
129.66/129.04 127.40-126.90 12 .times. C CH C3, C5 115.17 1 .times.
C CH C10 114.89 1 .times. C CH C8 114.83 1 .times. C CH C15 114.10
1 .times. C CH C17 95.64/94.85 2 .times. C C.sub.q C1, C1' 81.32 1
.times. C C.sub.q C25 55.08 1 .times. C CH.sub.3 C21 55.04 1
.times. C CH.sub.3 C18 35.25 1 .times. C C.sub.q C19 35.09 1
.times. C C.sub.q C22 30.77 3 .times. C CH.sub.3 C20 30.64 3
.times. C CH.sub.3 C23 27.56 3 .times. C CH.sub.3 C26
TABLE-US-00004 TABLE 4 Assignment of the .sup.1H chemical shifts of
2 .delta. [ppm] Intensity Multiplicity Assignment 7.54 4H m H3, H4,
H5 7.21 3H m H8, H10 7.09 5H m H15, H17 6.99-6.89 6H m 6.83 6H m
3.50 3H s H19 3.41 3H s H22 1.39 9H s H20 1.31 9H s H23 1.21 9H s
H26
Synthesis of Ligand 3
Reaction of tert-butyl
(3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy-[1,1'-biph-
enyl]-2-yl)carbonate with 2,2'-biphenol
##STR00019##
[0192] In a 250 ml Schlenk flask which had been repeatedly
evacuated and filled with inert gas, 10.5 g (0.019 mol) of
tert-butyl
(3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy-[1,1'-biph-
enyl]-2-yl)carbonate were dissolved in 50 ml of degassed
acetonitrile while stirring.
[0193] In a second Schlenk flask (250 ml) which had been repeatedly
evacuated and filled with inert gas, 3.6 g (0.019 mol) of
2,2'-biphenol were dissolved in 40 ml of degassed acetonitrile and
6.3 ml (0.045 mol) of dried triethylamine while stirring.
Subsequently, the chlorophosphite mixture was slowly added dropwise
at room temperature to the biphenol/triethylamine solution, and the
mixture was stirred at room temperature overnight. The resultant
solids were filtered and dried. The target product was obtained as
a white solid (11.5 g, 90%). .sup.31P NMR (202.4 MHz,
toluene-d.sub.8): 146.2 ppm (100%).
##STR00020##
TABLE-US-00005 TABLE 5 Assignment of the .sup.13C chemical shifts
of 3 .delta. [ppm] Intensity Group Assignment 157.46 1 .times. C
C.sub.q C16 155.51 1 .times. C C.sub.q C26 151.76 1 .times. C
C.sub.q C31 150.51/149.92 each 1 .times. C C.sub.q C1 + C8 144.07 1
.times. C C.sub.q C24 143.62 1 .times. C C.sub.q C13 142.70 1
.times. C C.sub.q C23 142.67 1 .times. C C.sub.q C14 135.75 1
.times. C C.sub.q C18 132.13/131.73 1 .times. C C.sub.q C6 + C7
131.30 1 .times. C C.sub.q C22 129.87/128.94 each 1 .times. C CH C5
+ C12 128.98/128.91 each 1 .times. C CH C3 + C10 125.16/124.98 each
1 .times. C CH C4 + C11 123.54/122.40 each 1 .times. C CH C2 + C9
115.14 1 .times. C CH C25 114.93 1 .times. C CH C15 114.85 1
.times. C CH C27 114.72 1 .times. C CH C17 81.36 1 .times. C
C.sub.q C32 55.14 1 .times. C CH.sub.3 C28 55.10 1 .times. C
CH.sub.3 C19 35.57 1 .times. C C.sub.q C29 35.22 1 .times. C
C.sub.q C20 30.78 3 .times. C CH.sub.3 C30 30.62 3 .times. C
CH.sub.3 C21 27.45 3 .times. C CH.sub.3 C33
TABLE-US-00006 TABLE 6 Assignment of the .sup.1H chemical shifts of
3 .delta. [ppm] Intensity Multiplicity Assignment 7.26 1H d (J =
7.7 Hz) H2, H9, H3, H10 7.15-7.09 6H m H5, H12, H15, H25 7.02 1H t
(J = 7.7 Hz) 6.95/6.91 2 .times. 1H 2 .times. t (J ~7.5 Hz) H4/H11
6.93 1H d (J = 3 Hz) H17 6.87 1H d (J = 3 Hz) H27 3.48 3H s H19
3.42 3H s H29 1.50 9H s H20 1.35 9H s H21 1.16 9H s H33
Synthesis of Ligand 4
Reaction of tert-butyl
(3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy-[1,1'-biph-
enyl]-2-yl)carbonate with 3,3,5,5-tetra-tert-butylbiphenol
##STR00021##
[0195] In a 250 ml Schlenk flask which had been repeatedly
evacuated and filled with inert gas, 7.0 g (0.0125 mol) of
tert-butyl
(3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy-[1,1'-biph-
enyl]-2-yl)carbonate were dissolved in 100 ml of dried
acetonitrile.
[0196] In a second Schlenk flask (100 ml) which had been repeatedly
evacuated and filled with inert gas, 5.1 g (0.0125 mol) of
3,3',5,5'-tetra-tert-butylbiphenol were dissolved in 60 ml of dried
acetonitrile and 4.2 ml (0.03 mol) of dried triethylamine while
stirring. Subsequently, the biphenol-triethylamine solution was
slowly added dropwise at room temperature to the chlorophosphite
solution and the mixture was stirred overnight. A portion of the
solvent was removed under reduced pressure. The precipitated solids
were filtered off and dried. The target product was obtained as a
white solid (10.2 g, 91%). .sup.31P NMR (202.4 MHz,
toluene-d.sub.8): 142.7 ppm (100%).
##STR00022##
TABLE-US-00007 TABLE 7 Assignment of the chemical shifts of 4
Number .delta.-.sup.1H/ppm .delta.-.sup.13C/ppm 1 -- 151.6 2 --
81.5 3 1.18 27.3 4 -- 142.3 5 -- 129.9 6 | 18 6.76 114.7 6.67 114.1
7 | 17 -- 154.4 156.8 8 | 16 6.93 113.5 6.88 115.4 9 -- 143.6 10 |
19 3.78 55.4 3.74 55.7 11 -- 35.0 12 1.39 30.6 21 | 29 | 31 | 39 |
41 1.03 31.2 1.24 31.0 1.29 31.4 1.34 31.5 1.39 30.7 1.48 31.3 13
-- 136.4 14 -- 142.1 15 -- 140.1 20 -- 34.6 22 | 32 -- 146.0 146.9
24 | 34 7.06 126.6 7.30 123.8 25 | 35 -- 145.1 146.3 26 | 36 7.08
126.3 7.42 124.1 28 | 38 -- 35.1 35.2 30 | 40 -- 34.6 35.4 23 | 33
-- 135.5 132.6 27 | 37 -- 140.0 141.9
Synthesis of Ligand 5
Reaction of tert-butyl
(3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy-[1,1'-biph-
enyl]-2-yl)carbonate with
3,3-di-tert-butyl-5,5-dimethoxybiphenol
##STR00023##
[0198] In a 250 ml Schlenk flask which had been repeatedly
evacuated and filled with inert gas, 7 g (0.0125 mol) of tert-butyl
(3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy-[1,1'-biph-
enyl]-2-yl)carbonate were dissolved in 100 ml of dried
acetonitrile.
[0199] In a second Schlenk flask (100 ml) which had been repeatedly
evacuated and filled with inert gas, 4.5 g (0.0125 mol) of
3,3-di-tert-butyl-5,5-dimethoxybiphenol were dissolved in 60 ml of
dried acetonitrile and 4.2 ml (0.03 mol) of degassed triethylamine.
Subsequently, the biphenol-triethylamine solution was slowly added
dropwise at room temperature to the chlorophosphite solution and
the mixture was stirred at room temperature overnight.
[0200] A portion of the solvent was removed under reduced pressure.
The precipitated solids were filtered off and dried. The target
product was obtained as a white solid (10.5 g, 96%). .sup.31P NMR
(202.4 MHz, toluene-d.sub.8): 140.9 (95.2%) and further impurities
(further impurities=P--H compounds, oxide compounds, as yet
incompletely converted chlorophosphite).
Synthesis of Ligand 11
Reaction of tert-butyl
(3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy[1,1'-biphe-
nyl]-2-yl)carbonate with 2,4-dimethylphenol
##STR00024##
[0202] In a 500 ml Schlenk flask which had been repeatedly
evacuated and filled with inert gas, 6.8 g (0.012 mol) of
tert-butyl
(3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy-[1,1'-biph-
enyl]-2-yl)carbonate were dissolved in 100 ml of dried
acetonitrile.
[0203] In a second Schlenk flask (250 ml) which had been repeatedly
evacuated and filled with inert gas, 6 g (6 ml; 0.048 mol) of
2,4-dimethylphenol were dissolved in 100 ml of dried acetonitrile
and 5 g (7 ml; 0.059 mol) of degassed triethylamine. Subsequently,
the biphenol-triethylamine solution was slowly added dropwise at
room temperature to the chlorophosphite solution and the mixture
was stirred at room temperature overnight and cooled in an ice bath
the next morning.
[0204] A portion of the solvent was removed under reduced pressure.
This formed a slime-like solution which solidified after prolonged
drying. The target product was obtained as a white solid (11.8 g,
62%). .sup.31P NMR (202.4 MHz, toluene-d.sub.8): 139.1 (92.8%) and
further impurities (further impurities=P--H compounds, oxide
compounds, as yet incompletely converted chlorophosphite).
Procedure for the Catalysis Experiments
Experiment Description
General
[0205] In a 100 ml autoclave from Parr Instruments, various olefins
were hydroformylated at various temperatures and synthesis gas
pressure 20 or 50 bar (CO/H.sub.2=1:1 (% by vol.)). As precursor,
0.005 g of Rh(acac)(CO).sub.2 was initially charged for a catalyst
concentration of 40 ppm of Rh based on the overall reaction
mixture, and correspondingly 0.0123 g of Rh(acac)(CO).sub.2 for a
concentration of 100 ppm of Rh. The solvent used was 40 to 46 g of
toluene in each case. Ligand 1 was used in different molar excesses
relative to rhodium. In addition, as GC standard, about 0.5 g of
tetraisopropylbenzene (TIPB) was added. About 6 g of reactant were
metered in after the reaction temperature envisaged had been
attained.
[0206] During the reaction, the pressure was kept constant via
metered addition of synthesis gas with a mass flow meter and
pressure regulator. The stirrer speed was 1200 min.sup.-1. Samples
were taken from the reaction mixture after 12 hours. The results of
the experiments are summarized in Table 8 (yield=total yield of
aldehyde and alcohol; S=selectivity for the linear product).
[0207] (acac=acetylacetonate)
TABLE-US-00008 TABLE 8 S Starting p cRh Yield (n-aldehyde) Entry
material in [bar] in ppm P:Rh in % in % 1 cis-2-butene 20 40 4 58.0
45.3 2 cis-2-butene 50 40 4 96.5 40.7 3 1-butene 20 40 4 49.2 51.9
4 1-butene 50 40 2 97.4 46.8 5 1-butene 50 92 8 99.5 50.3 6
1-octene 50 40 9 97.1 43.2 Reaction conditions: ligand 1, reaction
temperature: 120.degree. C.
[0208] Lines 1 and 2 list experiments on the rhodium-catalysed
hydroformylation of the cis-2-butene reactant with ligand 1. At a
synthesis gas pressure of 20 bar, in experiment 1, 58.0 mol % of
pentanal is formed with a pentanal selectivity of 45.3%. The
proportion of hydrogenation to the alkane is low at about 1.3% to
1.5%. The formation of pentanol is not observed. An increase in the
synthesis gas pressure leads to a rise in the pentanal yield to
95.1 mol %, but the regioselectivity falls to about 40%.
[0209] Lines 3 to 5 list hydroformylations of 1-butene. At 20 bar
(line 3), at a ligand excess of 4:1, a yield of about 49% and a
selectivity for n-pentanal of about 52% are attained. At synthesis
gas pressure 50 bar, a n-pentanal selectivity of 50% is obtained
with virtually full conversion (lines 4 and 5). Alkane formation is
low. In the experiment in line 4, the molar excess of ligand was
reduced to about 2:1. The yield rises to 97.4%; the pentanal
selectivity falls slightly to 46.8%. In line 5, the Rh
concentration was increased to about 100 ppm and the ligand excess
was increased to 8:1 relative to rhodium. The aldehyde yield rises
to 99.5%; the regioselectivity likewise rises to 50.3%.
[0210] It is also possible to hydroformylate longer-chain olefins
such as 1-octene with good n selectivity for the product (line
6).
[0211] Table 9 contains experiments on the hydroformylation of an
n-octene mixture having about 2% 1-octene, 40% 2-octenes, 36%
3-octenes and 23% 4-octenes (yield=total yield of aldehyde and
alcohol; S=selectivity for the linear n-pentanal product). In this
case, the experiments were conducted both with the inventive ligand
1 and with the comparative TDTBPP ligand.
##STR00025##
Tris(2,4-di-tert-butylphenyl)phosphite (TDTBPP)
TABLE-US-00009 [0212] TABLE 9 S (linear T cRh Yield product) Entry
in [.degree. C.] in ppm P:Rh in % in % 1.sup.a 80 90 20 99.0 7.2
2.sup.a 80 90 5 99.0 11.1 3.sup.a 90 90 20 99.2 10.6 4.sup.b 90 280
20 97.9 4.7 5.sup.a 100 50 20 99.0 15.4 6.sup.b 100 90 20 96.4 6.9
7.sup.a 110 90 20 99.2 16.5 8.sup.b 110 90 20 99.0 9.7 9.sup.a 120
90 20 95.2 22.9 10.sup.b 120 90 20 99.0 14.4 11.sup.a 130 90 20
98.0 30.5 12.sup.b 130 76 20 98.8 23.9 13.sup.a 140 90 20 97.4 31.6
14.sup.b 140 56 20 98.0 23.9 15.sup.a 120 90 4 98.9 28.8 16.sup.a
120 40 9.5 98.6 29.1 17.sup.a 120 40 20 99.1 28.2 Reaction
conditions: 50 bar of synthesis gas (CO/H.sub.2); substrate:
n-octenes; .sup.aligand 1; .sup.bligand TDTBPP.
[0213] Entries 1 to 14 each show results of experiments at a
constant temperature in the range from 80.degree. C. to 140.degree.
C., in each case for the inventive ligand 1 and for the comparative
ligand (TDTBPP). As is clearly apparent, the inventive ligand 1 in
all cases shows a distinctly higher n selectivity for the desired
product combined with very good overall yields. The formation of
alkanes and alcohols is insignificant. If entries 13 and 14 are
compared, ligand 1 has nearly an 8% increase in selectivity
compared to the commercially available comparative ligand. Entries
15 to 17 show the use of ligand 1 with different molar excesses
relative to rhodium. In all cases, it was possible to achieve very
good n selectivities.
[0214] Table 10 gives the results for the hydroformylation of
di-n-butene. Di-n-butene is a mixture of isomers of n-octenes
(about 16%), 3-methylheptenes (about 65%) and 3,4-dimethylhexenes
(about 19%) (yield=total yield of aldehyde and alcohol;
S=selectivity for the linear product).
TABLE-US-00010 TABLE 10 T p cRh Yield S (nl)* Entry in [.degree.
C.] in [bar] in ppm P:Rh in % in % 1 120 50 40 10 85.1 30.8 2 120
50 90 7 89.8 28.3 3 120 50 90 7 91.5 30.9 4 120 50 100 5 93.0 36.5
5 120 50 75 20 94.6 29.8 6 130 50 75 20 95.3 32.7 7 110 50 75 20
91.9 24.0 8 120 40 75 20 94.8 29.0 Reaction conditions: ligand 1;
substrate: di-n-butene *Proportion of the aldehydes formed through
terminal hydroformylation (essentially nonanal, 4-methyloctanal,
3-ethylheptanal, 6-methyloctanal, 4,5-dimethylheptanal and
3-ethyl-4-methylhexanal)
[0215] The above Table 10 contains experimental results for the
rhodium-catalysed hydroformylation of di-n-butene with ligand 1.
Entries 1 to 5 were conducted at 120.degree. C. and 50 bar, and
entry 8 at 40 bar. Entries 2 and 3 are a double determination with
a ligand excess of 7 relative to rhodium and a rhodium
concentration based on the overall reaction mixture of 80 ppm;
entry 1 was performed at an excess of about 10:1 and an Rh
concentration of 40 ppm. Entry 4 describes a reduction in the
excess to 5:1 compared to entries 2 and 3. Entries 5 to 8 are
experiments with a high ligand excess of about 20:1. Entries 5 to 7
were conducted at different temperatures. Entry 8 differs from
entry 5 by the pressure. Analogously to the experiments with the
n-octene mixture, high n selectivities between 28 and 36 mol % are
found in all of experiments 1 to 6 and 8. At lower temperature
(entry 7), the n selectivity is reduced to about 24%. n-Octenes are
converted virtually quantitatively within the experimental duration
of 12 hours; the conversion of the 3-methylheptenes is >96%. The
3,4-dimethylhexenes are converted to an extent of 73%-86%. It was
thus possible to show with the aid of the above examples that the
novel catalyst system is also suitable for hydroformylation of
technical olefin mixtures containing mainly branched olefins
containing internal double bonds, and a high proportion of desired
terminally hydroformylated products can be obtained.
[0216] Table 11 gives the results for the hydroformylation of
n-octenes with ligand 3 (yield=total yield of aldehyde and alcohol;
S=selectivity for the linear product).
TABLE-US-00011 TABLE 11 T Yield S (linear product) Entry in
[.degree. C.] in % in % 1 80 30.0 8.6 2 90 85.9 4.9 3 100 91.3 5.9
4 110 98.5 8.3 5 120 99.0 11.9 Reaction conditions: ligand 3; 50
bar of synthesis gas; substrate: n-octenes; cRh = 90 ppm; L/Rh =
20.
[0217] The above table contains a compilation of the experimental
data for the hydroformylation of n-octenes with ligand 3 in the
form of a temperature series from 80.degree. C. to 120.degree. C.
at synthesis gas pressure 50 bar, an Rh concentration of about 100
ppm and a ligand excess of about 20:1. The n-nonanal selectivities
in this series of experiments are low at 4.9 to 11.9 mol %, but the
aldehyde yields at higher temperatures are virtually quantitative
and very good. Alkane formation is low at <1%; hydrogenation to
alcohols is not observed.
[0218] Table 12 gives the results for the hydroformylation of
di-n-butene. Di-n-butene is a mixture of isomers of n-octenes
(about 16%), 3-methylheptenes (about 65%) and 3,4-dimethylhexenes
(about 19%) (yield=total yield of aldehyde and alcohol;
S=selectivity for the linear product).
TABLE-US-00012 TABLE 12 T p cRh Yield Entry Ligand in [.degree. C.]
in [bar] in ppm P:Rh in % 1 4 140 50 100 20:1 38 2 3 140 50 100
10:1 74 3 5 120 50 100 20:1 85 4 5 130 50 100 20:1 86 5 5 140 50
100 20:1 96 6 5 140 50 100 15:1 97 7 5 140 50 100 5:1 97 Reaction
conditions: ligand 1; substrate: di-n-butene * Proportion of the
aldehydes formed through terminal hydroformylation (essentially
nonanal, 4-methyloctanal, 3-ethylheptanal, 6-methyloctanal,
4,5-dimethylheptanal and 3-ethyl-4-methylhexanal)
[0219] The above Table 12 contains experimental results for the
rhodium-catalysed hydroformylation of di-n-butene with ligands 3, 4
and 5. While ligand 4 (entry 1) gives a moderate overall yield of
aldehydes and alcohols, ligands 3 and 5 are notable for very good
yields. Especially ligand 5 shows virtually quantitative yields at
elevated temperature (140.degree. C.) (entries 5 to 7).
[0220] It was thus possible to show with the aid of the above
examples that the novel catalyst system is also suitable for
hydroformylation of technical olefin mixtures containing mainly
branched olefins containing internal double bonds, and a high
proportion of desired hydroformylated products can be obtained.
[0221] The inventive monophosphite ligands have a very good n
selectivity in relation to the hydroformylation. Selectivity for
the desired linear aldehydes is much greater here than, for
example, in the case of the commercially available TDTBPP ligand.
The stated objects are therefore achieved by these novel inventive
ligands.
[0222] German patent application 102014209534.4 filed May 20, 2014,
is incorporated herein by reference.
[0223] Numerous modifications and variations on the present
invention are possible in light of the above teachings. It is
therefore to be understood that within the scope of the appended
claims, the invention may be practiced otherwise than as
specifically described herein.
* * * * *