Title of Invention

"A CATALYST SYSTEM USED IN CARBONYLATION OFAN ETHYLENICALLY UNSATURATED COMPOUND"

Abstract A catalyst system capable of catalysing the carbonylation of an ethylenically unsaturated compound, which system is obtainable by combining (a) a metal of Group VIB or Group VIIIB or a compound thereof, (b) a bidentate phosphine, arsine, or stibine ligand, and (c) an acid, wherein the carbonylation is carried out at between -10 to 150°C and a partial pressure of between 0.80 x 105Nm-2 - 90 x 105Nm"2 and wherein said ligand is present in at least a 2:1 molar excess compared to said metal or said metal in said metal compound, and that said acid is present in the range greater than 5:1 to 95:1 molar excess compared to said ligand; or wherein the ratio of said ligand to said metal or said metal in said metal compound is in the range 5:1 to 750:1, and that said acid is present at a greater than 2:1 molar excess compared to said ligand.
Full Text The present invention relates to a novel catalyst system,
a novel carbonylation reaction medium and a process for
the carbonylation of ethylenically unsaturated compounds
using a novel catalyst system.
The carbonylation of ethylenically unsaturated compounds
using carbon monoxide in the presence of an alcohol or
water and a catalyst system comprising a Group VIII metal,
eg. palladium, and a phosphine ligand eg. an alkyl
phosphine cycloalkyl phosphine, aryl . _p_hosphine, pyridyl
phosphine or bidentate phosphine, has been described in
numerous European patents and patent applications, eg. EPA-
0055875, EP-A-04489472, EP-A-0106379, EP-A-0235864, EPA-
0274795, EP-A-0499329, EP-A-0386833, EP-A-0441447, EP-A-
0489472, EP-A-0282142, EP-A-0227160, EP-A-0495547 and EPA-
0495548. In particular, EP-A-0227160, EP-A-0495547 and
EP-A-0495548 disclose that bidentate phosphine ligands
provide catalyst systems which enable higher reaction
rates to be achieved.
WO 96/19434 discloses a bridging group in the form of an
optionally substituted aryl moiety, linked to the said
phosphorous atoms via available adjacent carbon atoms on
the said aryl moiety. Such a ligand is more stable and
leads to reaction rates which are significantly higher
than those previously disclosed and produces little or no
impurities for the carbonylation of ethylene. Each
phosphorous atom in the said ligand is also linked to two
tertiary carbon atoms.
However, conventional metal-catalysed reactions, such as
those described in WO 96/19434 tend to suffer from the
drawback that the catalyst tends to de-activate over the
course of a period of continuous operation as the
palladium compound is reduced to palladium metal, this
contributing to the economic viability of the process.
01/10551 addressed this problem via the use of stabilising
compounds such as polymeric dispersants in the reaction
medium, thus improving in the recovery of metal which has
been lost from the catalyst system.
Although catalyst systems have been developed which
exhibit reasonable stability during the carbonylation
process and permit relatively high reaction rates to be
achieved, there still exists a need for improved catalyst
systems. Suitably, the present invention aims to provide
an improved catalyst for carbonylating ethylenically
unsaturated compounds.
J.Mol.Cat.A 204-205 (2003) pgs 295-303 suggests that a
relative increase in the ligand concentration, for example
by the addition of more ligand, has a detrimental effect
on productivity. Similar results are reported in
J.Mol.Cat.A.Chem. 110 (1996) pgs 13-23 and
J.Mol.Cat.A.Chem. 151 (2000) pgs 47-59.
Moreover, WO-A-01/72697 describes a process for the
carbonylation of pentenenitrile but teaches that there are
disadvantages associated at relatively high acid:palladium
ratios. The authors state that the disadvantages occur
because high acid concentration conditions are corrosive
and more ligand degradation results from quaternisation
with the acid and the olefinic compound.
WO-A-01/68583 discloses a process for the carbonylation of
ethylenically unsaturated compounds using phosphine-based
bidentate ligands. However, this disclosure is directed
towards the use of relatively low acid levels, leading to
low acid:ligand values. Moreover, the ligand:metal ratios
are low. WO-A-03/040159 similarly discloses low
acid:ligand and ligand:metal ratios.
WO-A-98/45040 discloses catalyst systems comprising
palladium compound and bidentate phosphorus ligands.
However, acid:ligand ratios of less than 1:1 are taught.
Finally, WO-A-01/72697 discloses a process for the
preparation of a 5-cyanovaleric acid by carbonylation of a
pentenenitrile. The disclosure points out the
disadvantages in using high acid concentrations and
teaches towards the use of relatively low acid levels.
Hence, an aim of the present invention is to seek to
establish a catalyst system wherein the levels of ligand
and acid are relatively high, but wherein the
disadvantages of the prior art noted hereinbefore are
addressed and alleviated, at least to some extent, the
aforesaid being one object of the present invention.
According to the present invention there is provided a
catalyst system, a process for the carbonylation of an
ethylenically unsaturated compound, a reaction medium, and
use as set forth in the appended claims.
Preferred features of the invention will be apparent from
the dependent claims, and the description which follows.
According to a first aspect, the present invention
provides a catalyst system capable of catalysing the
carbonylation of an ethylenically unsaturated compound,
which system is obtainable by combining:
a) a metal of Group VIB or Group VIIIB or a compound
thereof,
b) a bidentate phosphine, arsine, or stibine ligand,
preferably a bidentate phosphine ligand, and
c) an acid,
wherein said ligand is present in at least a 2:1 molar
excess compared to said metal or said metal in said metal
compound, and that said acid is present in at least a 2:1
molar excess compared to said ligand.
Typically, component b) is a bidentate phosphine, arsine,
or stibine.
Suitably, all of components a) to c) of the catalyst
system can be added in situ to the reaction vessel wherein
the carbonylation is to take place. Alternatively, the
components a) to c) can be added sequentially in any order
to form the catalyst system, or in some specified order,
either directly into the vessel or outside the vessel and
then added to the vessel. For instance, the acid
component c) may first be added to the bidentate ligand
component b) , to form a protonated ligand, and then the
protonated ligand can be added to the metal or compound
thereof (component a)) to form the catalyst system.
Alternatively, the ligand component b) and metal or
compound thereof (component a)) can be mixed to form a
chelated metal compound, and the acid (component c) ) is
then added. Alternatively, an~y two components can be
reacted together to form an intermediate moiety which is
then either added to the reaction vessel and the third
component added, or is first reacted with the third
component and then added to the rreaction vessel.
As such, the present invention d.s directed to a catalyst
system wherein the relative molar concentrations of both
the bidentate ligand and the add are at levels in excess
of those previously envisaged, .leading to surprising and
unexpected advantages when using the catalyst system in
the carbonylation of ethylenically unsaturated compounds,
and the alleviation or at least ireduction of at least some
of the disadvantages of the prior art systems. In
particular, the use of a catalyst system of the present
invention leads at least to a more stable system,
increased reaction rates, and improved turnover numbers in
carbonylation reactions of ethylenically unsaturated
compounds.
As stated above, the ligand is present in the catalyst
system, or precursor thereto, in such quantity that the
ratio of said ligand to the said metal (i.e. component b)
to component a)) is at lea.st a 2:1 molar ratio.
Preferably, the ratio of said ligand to the said metal is
greater than a 2:1 molar ratio, more preferably in the
range 2:1 to 1000:1, even mores preferably in the range
2.5:1 to 1000:1, yet more preferably in the range 3:1 to
1000:1, even more preferably in the range 5:1 to 750:1,
more preferably in the range 7:H to 1000:1, especially in
the range 8:1 to 900:1, still more preferably in the range
10:1 to 500:1, yet still more preferably in the range 20:1
to 400:1, even more preferably in the range 50:1 to 250:1,
most preferably in the range in excess of 50:1, for
example 51:1 and upwards, more specifically 51:1 to 250:1
or even to 1000:1. Alternatively, the said ratio can be
in the range 15:1 to 45:1, preferably 20:1 to 40:1, more
preferably 25:1 to 35:1.
As stated above, the acid is present in the catalyst
system, or precursor thereto, in such quantity that the
ratio of said acid to the said ligand (i.e. component c)
to component b)) is at least a 2:1 molar ratio.
Preferably, the ratio of said acid to the said ligand is
greater than a 2:1 molar ratio, more preferably in the
range 2:1 to 100:1, even more preferably in the range 4:1
to 100:1, yet more preferably in the range 5:1 to 95:1,
still more preferably in the range greater than 5:1 to
95:1, yet more preferably in the range greater than 5:1 to
75:1, more preferably in the range 10:1 to 50:1, even more
preferably in the range 20:1 to 40:1, still more
preferably in the range greater than 20:1 to 40:1 (e.g.
25:1 to 40:1, or 25:1 to less than 30:1), more preferably
in excess of 30:1, suitably with any of the upper limits
provided hereinbefore (e.g. 30:1 to 40:1, or 50:1, etc.),
or more preferably in excess of 35:1, yet more preferably
in excess of 37:1, suitably either with any of the upper
limits provided hereinbefore. Each of the ranges in this
paragraph can be used in conjunction with each of the
ligand to metal ratio ranges disclosed hereinabove, i.e.
ratios of component b) to component a).
By "acid", we mean an acid or salt thereof, and references
to acid should be construed accordingly.
The advantages in working within the ligand to metal, and
acid to ligand ratios, set out above are manifest in that
the stability of the catalyst system is improved, as
evidenced by increases in the turnover number (TON) of the
metal. By improving the stability of the catalyst system,
the usage of metal in the carbonylation reaction scheme is
kept to a minimum.
Without wishing to be bound by theory, it is believed that
by working within the specific ratio ranges noted herein,
it is surprisingly found that the ligand component of the
catalyst system is protected against inadvertent aerial
oxidation (in instances where there is any ingress of air
into the reaction system), and the overall stability of
the catalyst system is improved, thus keeping the usage of
the metal component of the catalyst system to a minimum.
Moreover, the forward reaction rate of the reaction is
surprisingly improved.
In effect, the level of acid should be such that for the
particular bidentate ligand employed, the level of acid
should be such that phosphine, arsine or stibine is fully
protonated. Hence, to show the improved effects, the
level of ligand should be above some, minimum level, as
given by the ligand:metal molar ratio, and the level of
acid should be above some minimum level with respect to
the level of ligand present to encourage protonation, as
given by the acid:ligand molar ratio.
Preferably, the acid is present in the catalyst system, or
precursor thereto, in such quantity that the molar ratio
of said acid to said metal (i.e. component c) to component
a)) is at least 4:1, more preferably from 4:1 to 100000:1,
even more preferably 10:1 to 75000:1, yet more preferably
20:1 to 50000:1, yet still more preferably 25:1 to
50000:1, yet still more preferably 30:1 to 50000:1, yet
even more preferably 40:1 to 40000:1, still more
preferably 100:1 to 25000:1, more preferably 120:1 to
25000:1, more preferably 140:1 to 25000:1, yet still more
preferably 200:1 to 25000:1, most preferably 550:1 to
20000:1, or greater than 2000:1 to 20000:1.
Alternatively, the said ratio can be in the range 125:1 to
485:1, more preferably 150:1 to 450:1, even more
preferably 175:1 to 425:1, yet even more preferably 200:1
to 400:1, most preferably 225:1 to 375:1. Each of these
ranges in this paragraph can be used in conjunction with
each of the ligand to metal ratio ranges disclosed
hereinabove, i.e. ratios of component b) to component a),
and/or each of the acid to ligand ratio ranges disclosed
hereinabove, i.e. ratios of component c) to component b).
For the avoidance of any doubt, .all of the aforementioned
ratios and ratio ranges apply to all of the ligand
embodiments set out in more detail hereinafter.
In one embodiment of the present invention, the bidentate
phosphine ligand is of general formula (I)
(Figure Removed)
wherein:
Ar is a bridging group comprising an optionally
substituted aryl moiety to which the phosphorus atoms are
linked on available adjacent carbon atoms;
A and B each independently represent lower alkylene;
K, D, E and Z are substituents of the aryl moiety (Ar) and
each independently represent hydrogen, lower alkyl, aryl,
Het, halo, cyano, nitro, OR19, OC(0)R20, C(O)R21, C(0)OR22,
NR23R24, C(0)NR25R26, C(S)R25R26, SR27, C(O)SR27, or -JQ3(
CR13(R14) (R15)CR16(R17) (R18) where J represents lower
alkylene; or two adjacent groups selected from K, Z, D and
E together with the carbon atoms of the aryl ring to which
they are attached form a further phenyl ring, which is
optionally substituted by one or more substituents
selected from hydrogen, lower alkyl, halo, cyano, nitro,
OR19, OC(0)R20, C(0)R21, C(0)OR22, NR23R2 C(S)R25R26, SR27 or C(0)SR27;
R13 to R18 each independently represent hydrogen, lower
alkyl, aryl, or Het, preferably each independently
represent lower alkyl, aryl, or Het;
R19 to R27 each independently represent hydrogen, lower
alkyl, aryl or Het;
R1 to R12 each independently represent hydrogen, lower
alkyl, aryl, or Het, preferably each independently
represent lower alkyl, aryl, or Het;
Q1, Q2 and Q3 (when present) each independently represent
phosphorous, arsenic or antimony and in the latter two
cases references to phosphine or phosphorous above are
amended accordingly, with preferably both Q1 and Q2
representing phosphorus, more preferably all of Q1, Q2 and
Q3 (when present) representing phosphorus.
Suitably, the bidentate phosphines of the invention should
preferably be capable of bidentate coordination to the
Group VIB or Group VIIIB metal or compound thereof, more
preferably to the preferred palladium.
Preferably, when K, D, E or Z represent -JQ3(
CR13(R14) (R15) )CR16(R17) (R18) , the respective K, D, E or Z
is on the aryl carbon adjacent the aryl carbon to which A
or B is connected or, if not so adjacent, is adjacent a
remaining K, D, E or Z group which itself represents -JQ3
(CR13 (R14) (R15)) CR" (R17) (R18) .
Specific but non-limiting examples of bidentate ligands
within this embodiment include the following: 1,2-bis-(ditert-
butylphosphinomethyl)benzene, 1,2-bis- (di-tertpentylphosphinomethyl)
benzene, 1,2-bis- (di-tertbutylphosphinomethyl)
naphthalene. Nevertheless, the
skilled person in the art would appreciate that other
bidentate ligands can be envisaged without departing from
the scope of the invention.
The term wAr" or "aryl" when used herein, includes
five-to-ten-membered, preferably, six-to-ten membered
carbocyclic aromatic groups, such as phenyl and naphthyl,
which groups are optionally substituted with, in addition
to K, D, E or Z, one or more substituents selected from
aryl, lower alkyl (which alkyl group may itself be
optionally substituted or terminated as defined below) ,
Het, halo, cyano, nitro, OR19, OC(0)R20, C(0)R21, C(O)OR22,
NR23R24, C(0)NR25R26, SR27, C (O) SR27 or C(S)NR2SR26 wherein R19
to R27 each independently represent hydrogen, aryl or
lower alkyl (which alkyl group may itself be optionally
substituted or terminated as defined below). Furthermore,
the aryl moiety may be a fused polycyclic group, e.g.
naphthalene, biphenylene or indene.
By the term "a metal of Group VIB or Group VIIIB" we
include metals such as Cr, Mo, W, Fe, Co, Ni, Ru, Rh, Os,
Ir, Pt and Pd. Preferably, the metals are selected from
Ni, Pt and Pd. More preferably, the metal is Pd. For the
avoidance of doubt, references to Group VIB or VIIIB
metals herein should be taken to include Groups 6, 8, 9
and 10 in the modern periodic table nomenclature.
The term "Het", when used herein, includes four-to-twelvemembered,
preferably four-to-ten-membered ring systems,
which rings contain one or more heteroatoms selected from
nitrogen, oxygen, sulphur and mixtures thereof, and which
rings may contain one or more double bonds or be nonaromatic,
partly aromatic or wholly aromatic in character.
The ring systems may be monocyclic, bicyclic or fused.
Each wHet" group identified herein is optionally
substituted by one or more substituents selected from
halo, cyano, nitro, oxo, lower alkyl (which alkyl group
may itself be optionally substituted or terminated as
defined below) OR19, OC(0)R20, C(0)R21, C(0)OR22, NR23R24,
C(0)NR25R26, SR27, C(0)SR27 or C(S)NR25R26 wherein R19 to R27
each independently represent hydrogen, aryl or lower alkyl
(which alkyl group itself may be optionally substituted or
terminated as defined below). The term "Het" thus includes
groups such as optionally substituted azetidinyl,
pyrrolidinyl, imidazolyl, indolyl, furanyl, oxazolyl,
isoxazolyl, oxadiazolyl, thiazolyl, thiadiazolyl,
triazolyl, oxatriazolyl, thiatriazolyl, pyridazinyl,
morpholinyl, pyrimidinyl, pyrazinyl, quinolinyl,
isoquinolinyl, piperidinyl/ pyrazolyl and piperazinyl.
Substitution at Het may be at a carbon atom of the Het
ring or, where appropriate, at one or more of the
heteroatoms.
"Het" groups may also be in the form of an N oxide.
The term "lower alkyl" when used herein, means Ci to CIQ
alkyl and includes methyl, ethyl, propyl, butyl, pentyl,
hexyl and heptyl groups. Unless otherwise specified, alkyl
groups may, when there is a sufficient number of carbon
atoms, be linear or branched, be saturated or unsaturated,
be cyclic, acyclic or part cyclic/acyclic, and/or be
substituted or terminated by one or more substituents
selected from halo, cyano, nitro, OR19, OC(0)R20, C(0)R21,
C(O)OR22, NR23R24, C(0)NR25R26, SR27, C(0)SR27, C(S)NR25R26,
aryl or Het, wherein R19 to R27 each independently
represent hydrogen, aryl or lower alkyl, and/or be
interrupted by one or more oxygen or sulphur atoms, or by
silano or dialkylsilcon groups.
Lower alkyl groups or alkyl groups which R1, R2, R3, (Figure Removed)
Z may
represent and with which aryl and Het may be substituted,
may, when there is a sufficient number of carbon atoms, be
linear or branched, be saturated or unsaturated, be
cyclic, acyclic or part cyclic/acyclic, and/or be
interrupted by one or more of oxygen or sulphur atoms, or
by silano or dialkylsilicon groups, and/or be substituted
by one or more substituents selected from halo, cyano,
nitro, OR19, OC(0)R20, C(0)R21, C(0)OR22, NR23R24, C(0)NR25R26,
SR27, C(O)SR27, C(S)NR25R2€, aryl or Het wherein R19 to R27
each independently represent hydrogen, aryl or lower
alkyl.
Similarly, the term "lower alkylene" which A, B and
(when present) represent in a compound of formula I, when
used herein, includes Ci to Ci0 groups which are bonded to
other moieties at least at two places on the group and is
otherwise defined in the same way as "lower alkyl".
Halo groups with which the above-mentioned groups may be
substituted or terminated include fluoro, chloro, bromo
and iodo.
Where a compound of a formula herein contains an alkenyl
group, cis (E) and trans (Z) isomerism may also occur. The
present invention includes the individual stereoisomers of
the compounds of any of the formulas defined herein and,
where appropriate, the individual tautomeric forms
thereof, together with mixtures thereof. Separation of
diastereoisomers or cis and trans isomers may be achieved
by conventional techniques, e.g. by fractional
crystallisation, chromatography or H.P.L.C. of a
stereoisomeric mixture of a compound one of the formulas
or a suitable salt or derivative thereof. An individual
enantiomer of a compound of one of the formulas may also
be prepared from a corresponding optically pure
intermediate or by resolution, such as by H.P.L.C. of the
corresponding racemate using a suitable chiral support or
by fractional crystallisation of the diastereoisomeric
salts formed by reaction of the corresponding racemate
with a suitable optically active acid or base, as
appropriate.
All stereoisomers are included within the scope of the
process of the invention.
It will be appreciated by those skilled in the art that
the compounds of formula I may function as ligands that
coordinate with the Group VIB or Group VIIIB metal or
compound thereof in the formation of the catalyst system
of the invention. Typically, the Group VIB or Group VIIIB
metal or compound thereof coordinates to the one or more
phosphorous, arsenic and/or antimony atoms of the compound
of formula I.
Preferably, R1 to R18 each independently represent lower
alkyl or aryl. More preferably, R1 to R18 each
independently represent Ci to Ce alkyl, Ci-Ce alkyl phenyl
(wherein the phenyl group is optionally substituted as
defined herein) or phenyl (wherein the phenyl group is
optionally substituted as defined herein). Even more
preferably, R1 to R18 each independently represent Ci to C6
alkyl, which is optionally substituted as defined herein.
Most preferably, R1 to R18 each represent non-substituted
Ci to Ce alkyl such as methyl, ethyl, n-propyl, iso-propyl,
n-butyl, iso-butyl, tert-butyl, pentyl, hexyl and
cyclohexyl.
Alternatively, or additionally, each of the groups R1 to
R3, R* to R6, R7 to R9, R10 to R12, R13 to R15 or R16 to R18
together independently may form cyclic structures such as
1-norbornyl or 1-norbornadienyl. Further examples of
composite groups include cyclic structures formed between
R^R18. Alternatively, one or more of the groups may
represent a solid phase to which the ligand is attached.
In a particularly preferred embodiment of the present
invention R1, R4, R7, R10, R13 and R16 each represent the
same lower alkyl, aryl or Het moiety as defined herein,
R2, R5, R8, R11, R14 and R17 each represent the same lower
alkyl, aryl or Het moiety as defined herein, and R3, R6,
R9, R12, R15 and R18 each represent the same lower alkyl,
aryl or Het moiety as defined herein. More preferably R1,
R4, R7, R10, R13 and R16 each represent the same Ci-C6 alkyl,
particularly non-substituted Ci-Ce alkyl, such as methyl,
ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tertbutyl,
pentyl, hexyl or cyclohexyl; R2, R5, R8, R11, R14 and
R17 each independently represent the same Ci-C6 alkyl as
defined above; and R3, R6, R9, R12, R15 and R18 each
independently represent the same Ci-Ce alkyl as defined
above. For example: R1, R4, R7, R10, R13 and R16 each
represent methyl; R2, R5, R8, R11, R14 and R17 each represent
ethyl; and, R3, R6, R9, R12, R15 and R18 each represent nbutyl
or n-pentyl.
In an especially preferred embodiment of the present
invention each R1 to R18 group represents the same lower
alkyl, aryl, or Het moiety as defined herein. Preferably,
each R1 to R18 represents the same Ci to C6 alkyl group,
particularly non-substituted Ci-Ce alkyl, such as methyl,
ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tertbutyl,
pentyl, hexyl and cyclohexyl. Most preferably, each
R1 to R18 represents methyl.
In the compound of formula I, preferably each Q1, Q2 and Q3
(when present) are the same. Most preferably, each Q1, Q2
and Q3 (when present) represents phosphorous.
Preferably, in the compound of formula I, A, B and J (when
present) each independently represent Ci to C6 alkylene
which is optionally substituted as defined herein, for
example with lower alkyl groups. Preferably, the lower
alkylene groups which A, B and J (when present) represent
are non-substituted. A particular preferred lower alkylene
which A, B and J may independently represent is -CHa- or -
CaH-. Most preferably, each of A, B and J (when present)
represent the same lower alkylene as defined herein,
particularly -
Preferably, in the compound of formula I when K, D, E or Z
does not represent -J-Q3(CR13(R14) (R15) )CR16 (R17) (R18) , K, D,
E or Z represents hydrogen, lower alkyl, phenyl or lower
alkylphenyl. More preferably, K, D, E or Z represent
hydrogen, phenyl, Ci-Ce alkylphenyl or Ci-Ce alkyl, such as
methyl, ethyl, propyl, butyl, pentyl and hexyl. Most
preferably, K, D, E or Z represents hydrogen.
Preferably, in the compound of formula I when K, D, E and
Z together with the carbon atoms of the aryl ring to which
they are attached do not form a phenyl ring, K, D, E and Z
each independently represent hydrogen, lower alkyl, phenyl
or lower alkylphenyl. More preferably, K, D, E and Z each
independently represent hydrogen, phenyl, Ci-C6
alkylphenyl or Ci-Ce alkyl, such as methyl, ethyl, propyl,
butyl, pentyl and hexyl. Even more preferably, K, D, E and
Z represent the same substituent. Most preferably, they
represent hydrogen.
Preferably, in the compound of formula I when K, D, E or Z
does not represent -J-Q3(CR13(R14) (R15) )CR16(R17) (R18) and K,
D, E and Z together with the carbon atoms of the aryl ring
to which they are attached do not form a phenyl ring, each
of K, D, E and Z represent the same group selected from
hydrogen, lower alkyl, aryl, or Het as defined herein;
particularly hydrogen or Ca-Ce alkyl (more particularly
unsubstituted Ci-Cg alkyl), especially hydrogen.
Preferably, in the compound of formula I when two of K, D,
E and Z together with the carbon atoms of the aryl ring to
which they are attached form a phenyl ring, then the
phenyl ring is optionally substituted with one or more
substituents selected from aryl, lower alkyl (which alkyl
group may itself be optionally substituted or terminated
as defined below), Het, halo., cyano, nitro, OR19, OC(0)R20,
C(O)R21, C(O)OR22, NR23R24, C(0)NR25R26, SR27, C(0)SR27 or
C(S)NR25R26 wherein R19 to R27 each independently represent
hydrogen or lower alkyl (which alkyl group may itself be
optionally substituted or terminated as defined herein).
More preferably, the phenyl ring is not substituted by any
substituents i.e. it bears hydrogen atoms only.
Preferred compounds of formula I include those wherein:
A and B each independently represent unsubstituted Ci to
Ce alkylene;
K, D, Z and E each independently represent hydrogen, Ci-C6
alkyl, phenyl, Ci-Ce alkylphenyl or -JQ3(
CR13(R14) (R15) )CR16(R17) (R18) where J represents
unsubstituted Ci to Cg alkylene; or two of K, D, Z and E
together with the carbon atoms of the aryl ring to which
they are attached form a phenyl ring which is optionally
substituted by one or more substituents selected from
lower alkyl, phenyl or lower alkylphenyl.
R1 to R18 each independently represent Ci to Ce alkyl,
phenyl or Ci to Ce alkylphenyl.
Further preferred compounds of formula I include those
wherein:
A and B both represent -CH2- or CjHo particularly
K, D, Z and E each independently represent hydrogen, Ci-Ce
alkyl phenyl or Ci-C6 alkyl or -JQ3(
CR13(R14) (R15) )CR16(R17) (R18) where J is the same as A; or
two of K, Df E and Z together with the carbon atoms of the
aryl ring to which they are attached form an unsubstituted
phenyl ring;
R1 to R18 each independently represent Ci to Ce alkyl;
Still further preferred compounds of formula I include
those wherein:
R1 to R18 are the same and each represents Ci to C6 alkyl,
particularly methyl.
Still further preferred compounds of formula I include
those wherein:
K, D, Z and E are each independently selected from the
group consisting of hydrogen or Ci to C6 alkyl,
particularly where each of K, D, Z and E represent the
same group, especially where each of K, D, Z and E
represent hydrogen; or
K represents -CH2-Q3 (CR13(R14) (R15) }CR16(R17) (R18) and D, Z
and E are each independently selected from the group
consisting of hydrogen or Ci to Ce alkyl, particularly
where both D and E represent the same group, especially
where D, Z and E represent hydrogen.
Especially preferred specific compounds of formula I
include those wherein:
each R1 to R12 is the same and represents methyl;
A and B are the same and represent -CHa-;
K, D, Z and E are the same and represent hydrogen.
In a still further embodiment, at least one (CRxRyRz) group
attached to Q1 and/or Q2, i.e. CR^R3, CR4R5R6, CR7R8R9, or
CR10R11R12, may instead be represented by the group (Ad)
wherein:
Ad each independently represent an optionally substituted
adamantyl or congressyl radical bonded to the phosphorous
atom via any one of its tertiary carbon atoms, the said
optional substitution being by one or more substituents
selected from hydrogen, lower alkyl, halo, cyano, nitro,
OR19, OC(0)R20, C(0)R21, C(0)OR22, NR23R24, C(0)NR25 R26,
C(S)R25R26, SR27 or C(0)SR27; or if both (CRxRyRz) groups
attached to either or both Q1 and/or Q2, or Q3 (if present)
together with either Q1 or Q2 (or Q3) as appropriate, form
an optionally substituted 2-phosphatricyclo[
3.3.1.1{3,7}]decyl group or derivative thereof,
or form a ring system of formula
wherein
R49, and R54, each independently represent hydrogen, lower
alkyl or aryl;
R50 to R53, when present, each independently represent
hydrogen, lower alkyl, aryl or Het; and
Y represents oxygen, sulfur or N-R55; and R55, when
present, represents hydrogen, lower alkyl or aryl.
In this embodiment, formula I may be represented as:
(Ad) s (CR7R8R9) TQ2~A- (K, D) Ar (E, Z) -B-Q1 (Ad) u (CR^R3) v
wherein Ar, A, B, K, D, E and Z, Q1, Q2, and Q3, and R1 to
R27 are as defined hereinbefore except that K, D, E and Z
may represent -J-Q3 (Ad)w(CR13 (R14) (R15)x instead of -JQ3(
CR13(R14) (R15) )CR16(R17) (R18) and Ad is as defined above,
S & U = 0 , I o r 2 provided that S + U ^ 1;
T & V = 0, 1 or 2 provided that T + V ^ 3;
W & X = 0, 1 or 2.
In addition to the preferred embodiments for R1 to R18, Q1
to Q3, A, B, J (when present), K, D, E or Z, R19 to R27,
noted hereinbefore/ all of which equally apply to the
present embodiment where at least one (Ad) group is
present, the following also applies.
Further preferred compounds of formula I include those
wherein:
A and B both represent -CH2- or -C2H4-, particularly -CH2-;
K, D, Z and E each independently represent hydrogen, Ci-C6
alkyl phenyl or d-C6 alkyl or -J-Q3 (Ad)w(CR13(R14) (R15) )x
where J is the same as A; or two of K, D, E and Z together
with the carbon atoms of the aryl ring to which they are
attached form an unsubstituted phenyl ring;
R1 to R3, R7 to R9, and R13 to R15 (when present) each
independently represent Ci to Ce alkyl, and the total
number of (Ad) groups attached to Q1 and Q2 is £ 3, i.e. S
+ U £ 3, and W and X = 0, 1 or 2.
Still further preferred compounds of formula I include
those wherein:
R1 to R3, R7 to R9 and R13 to R15 (when present) are the
same and each represents Ci to Ce alkyl, particularly
methyl, and the total number of (Ad) groups attached to Q1
and Q 2is^3, i.e. S + U £ 3 .
Still further preferred compounds of formula I include
those wherein :
K, D, Z and E are each independently selected from the
jroup consisting of hydrogen or Ci to Ce alkyl,
particularly where each of K, D, Z and E represent the
same group, especially where each of K, D, Z and E
represent hydrogen; or
K represents -CH2-Q3 (Ad)w(CR13(R14) {R15)x and D, Z and E are
each independently selected from the group consisting of
hydrogen or Ci to Ce alkyl, particularly where both D and
E represent the same group, especially where D, Z and E
represent hydrogen, wherein W and X = 0, 1 or 2.
Especially preferred specific compounds of formula I
include those wherein:
each R1 to R3, and R7 to R9 is the same and represents
methyl or the total number of (Ad) groups attached to Q1
and Q2 is 2, i.e. S + U = 2;
A and B are the same and represent -CH2-;
K, D, Z and E are the same and represent hydrogen.
Especially preferred specific compounds of formula I
include those wherein Ad is joined to Qi or Q2 at the same
position in each case. Preferably S £ 1 and U ^ 1, more
preferably, S = 2 and U ^ 1 or vice versa, most preferably
S & U = 2, wherein S is the number of (Ad) groups attached
to Q2 and U is the number of (Ad) groups attached to Q1.
Specific but non-limiting examples of bidentate ligands
within this embodiment include the following: 1,2
bis (diadamantylphosphinomethyl)benzene, 1,2 bis(di-3,5-
dimethyladamantylphosphinomethyl) benzene, 1,2 bis(di-5-
tert-butyladamantaylphosphinomethyl) benzene, 1,2 bis(ladamantyl
tert-butyl-phosphinomethyl)benzene, 1,2 bis(di-
1-diamantanephosphinomethyl) benzene, 1-
l-(di-tertl-(
di-tert-
1-
t(diadaraantylphosphinomethyl)-2-(di-tertbutylphosphinomethyl)
]benzene,
butylphosphinomethyl)-2-
(dicongressylphosphinomethyl)benzene,
butylphosphinomethyl) -2-(phosphaadamantylphosphinomethyl)
benzene,
(diadamantylphosphinomethyl) -2- (phosphaadamantylphosphinomethyl)
benzene, 1-(tert-butyladamantyl)-
2-(di-adamantyl)-(phosphinomethyl)benzene and 1-[(P-
(2,2, 6, 6,-tetra-methylphosphinan-4-one)phosphinomethyl) ]-
2-(phospha-adamantylphosphinomethyl)benzene.
Nevertheless, the skilled person in the art would
appreciate that other bidentate ligands can be envisaged
without departing from the scope of the invention.
In a yet further embodiment, the bidentate phosphine
ligand is of general formula (III) .
wherein:
AI and A2, and A3, A4 and A5 (when
independently represent lower alkylene;
present) , each
K1 is selected from the group consisting of hydrogen,
lower alkyl, aryl, Het, halo, cyano, nitro, -OR19,
OC(0)R20, -C(0)R21, -C(0)OR22, -N(R23)R24, -C (O) N (R25) R26, -
C(S) (R27)R28, -SR29, -C(0)SR30, -CF3 or -A3-Q3 (Xs) X6;
D1 is selected from the group consisting of hydrogen,
lower alkyl, aryl, Het, halo, cyano, nitro, -OR19,
OC(0)R*°, -C(0)R21, -C(0)OR22, -N(R23)R24, -C (0) N (R25) R26, -
C(S) (R27)R28, -SR29, -C(0)SR30, -CF3 or -A4-Q4 (X7) X8;
E1 is selected from the group consisting of hydrogen,
lower alkyl, aryl, Het, halo, cyano, nitro, -OR19,
OC(0)R20, -C(O)R21, -C(O)OR22, -N(R23)R24, -C (O) N (R25) R26, -
C(S) (R27)R28, -SR29, -C(0)SR30, -CF3 or -A5-Q5 (X9) X10;
or both D1 and E1 together with the carbon atoms of the
cyclopentadienyl ring to which they are attached form an
optionally substituted phenyl ring:
X1 represents CR1(R2)(R3 ) , congressyl or adamantyl, X2
represents CR4(R5 ) ( R 6 ) , congressyl or adamantyl, or X1 and
X2 together with Q2 to which they are attached form an
optionally substituted 2-phosphatricyclo[
3.3.1.1(3,7}]decyl group or derivative thereof,
or X1 and X2 together with Q2 to which they are attached
form a ring system of formula Ilia
(Formula Removed)
X3 represents CR7(R8)(R9), congressyl or adamantyl, X4
represents CR10(R11) (R12), congressyl or adamantyl, or X3
and X4 together with Q1 to which they are attached form an
optionally substituted 2-phosphatricyclo[
3.3.1.1(3,7}]decyl group or derivative thereof,
or X3 and X4 together with Q1 to which they are attached
form a ring system of formula Illb
(Formula Removed)
X5 represents CR13(R14) (R15) , congressyl or adamantyl, X6
represents CRI6(R17) (R18), congressyl or adamantyl, or X5
and X6 together with Q3 to which they are attached form an
optionally substituted 2-phosphatricyclo[
3.3.1.1(3,7}]decyl group or derivative thereof,
or X5 and X6 together with Q3 to which they are attached
form a ring system of formula IIIc
(Formula Removed)
X7 represents CR31 (R32) (R33), congressyl or adamantyl, X8
represents CR34 (R35) (R36), congressyl or adamantyl, or X7
and X8 together with Q4 to which they are attached form an
optionally substituted 2-phosphatricyclo[
3.3.1.1{3/7}]decyl group or derivative thereof,
or X7 and X8 together with Q4 to which they are attached
form a ring system of formula Hid
(Formula Removed)
X9 represents CR37 (R38) (R39), congressyl or adamantyl, X10
represents CR40(R41) (R42), congressyl or adamantyl, or X9
and X10 together with Qs to which they are attached form an
optionally substituted 2-phosphatricyclo[
3.3.1.1.{3,7}]decyl group or derivative thereof,
or X9 and X10 together with Q5 to which they are attached
form a ring system of formula Hie
and in this yet further embodiment,
Q1 and Q2, and Q3, Q4 and Q5 (when present), each
independently represent phosphorus, arsenic or antimony;
M represents a Group VIB or VIIIB metal or metal cation
thereof;
LI represents an optionally substituted cyclopentadienyl,
indenyl or aryl group;
L2 represents one or more ligands each of which are
independently selected from hydrogen, lower alkyl,
alkylaryl, halo, CO, P (R43) (R44)R45 or N(R46) (R47)R48;
R1 to R18 and R31 to R42, when present, each independently
represent hydrogen, lower alkyl, aryl, halo or Het;
R19 to R30 and R43 to R48, when present, each independently
represent hydrogen, lower alkyl, aryl or Het;
R49, R54 and R55, when present, each independently represent
hydrogen, lower alkyl or aryl;
R50 to R53, when present, each independently represent
hydrogen, lower alkyl, aryl or Het;
Y1, Y2, Y3, Y4 and Y5, when present, each independently
represent oxygen, sulfur or N-R55;
n = 0 or 1;
and m = 0 to 5;
provided that when n = 1 then m equals 0, and when n
equals 0 then m does not equal 0.
Preferably in a compound of formula III when both K1
represents -A3-Q3(X5)X6 and E1 represents -A5-Q5 (X9) X10, then
D1 represents -A4-Q4 (X7) X8.
Preferably, in this embodiment, R1 to R18 and R31 to R42,
when present, each independently represent hydrogen,
optionally substituted Ci to Ce alkyl, Ci-Ce alkyl phenyl
(wherein the phenyl group is optionally substituted as
defined herein), trifluoromethyl or phenyl (wherein the
phenyl group is optionally substituted as defined herein) .
Even more preferably, R1 to R18 and R31 to R42, when
present, each independently represent hydrogen, Ci to Ce
alkyl, which is optionally substituted as defined herein,
trifluoromethyl or optionally substituted phenyl. Even
more preferably, R1 to R18 and R31 to R42, when present each
independently represent hydrogen, non-substituted Ci to Ce
alkyl or phenyl which is optionally substituted with one
or more substituents selected from non-substituted Ci to
Ce alkyl or OR19 where R19 represents hydrogen or
unsubstituted Ci to Ce alkyl. More preferably, R1 to R18
and R31 to R42, when present, each independently represent
hydrogen or non-substituted Ci to Ce alkyl such as methyl,
ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tertbutyl,
pentyl, hexyl and cyclohexyl, especially metlnyl.
Most preferably, R1 to R18 and R31 to R42 when present, each
independently represent non-substituted Ci to Ce alkyl such
as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl,
tert-butyl, pentyl, hexyl and cyclohexyl,
especially methyl.
Alternatively, or additionally, one or more of the groups
R1 to R3, R4 to R6, R7 to R9, R10 to R12, R13 to R15, R16 to
R18, R31 to R33, R34 to R36, R37 to R39 or R40 to R42 (when
present) together with the carbon atom to which they are
attached independently may form cyclic alkyl structures
such as 1-norbornyl or 1-norbornadienyl.
Alternatively, or additionally, one or more of the groups
R1 and R2, R4 and R5, R7 and R8, R10 and R11, R13 and R14, R16
and R17, R31 and R32, R34 and R35, R37 and R38 or R40 and R41
(when present) together with the carbon atom to which they
are attached, independently may form a cyclic alkyl
structures, preferably a C5 to C7 cyclic alkyl structure
such as cyclohexyl and cyclopentyl, and R3, R6, R9, R12,
R15, R18, R33, R36, R39 and R42 (when present) each
independently represent hydrogen, lower alkyl,
trifluoromethyl or aryl as defined above, particularly
non-substituted Ci to Ce alkyl and hydrogen, especially
non-substituted Cj. to Ce alkyl.
In an especially preferred embodiment, each of R1 to R18
and R31 to R42, when present, do not represent hydrogen.
Suitably, such an arrangement means Q1, Q2, Q3, Q4 and Q5
are bonded to a carbon atom of X1 to X10, respectively,
which bears no hydrogen atoms.
Preferably, R1, R4, R7, R10, R13, R16, R31, R34, R37 and R40
(when present) , each represent the same substituent as
defined herein; R2, R5, R8, R11, R14, R17, R32, R35, R38 and
R41 (when present), each represent the same substituent as
defined herein; and R3, R6, R9, R12, R15, R18, R33, R36, R39
and R42 (when present), each represent the same
substituent as defined herein. More preferably R1, R4, R7,
R10, R13, R16, R31, R34, R37 and R40 (when present) each
represent the same Ci-C6 alkyl, particularly nonsubstituted
Ci-Ce alkyl, such as methyl, ethyl, n-propyl,
iso-propyl, n-butyl, iso-butyl, tert-butyl, pentyl, hexyl
or cyclohexyl, or trifluoromethyl; R2, R5, R8' R11, R14, R17,
R32, R35, R38 and R41 (when present) , each independently
represent the same Ci-Ce alkyl as defined above, or
trifluoromethyl; and R3, R6, R9, R12, R15, R18, R33, R36, R39
and R42 (when present), each independently represent the
same Ci-Ce alkyl as defined above, or trifluoromethyl. For
example: R1, R4, R7, R10, R13 and R16 (when present) each
represent methyl; R2, R5, R8, R11, R14 and R17 each represent
ethyl (when present); and, R3, R6, R9, R12, R15 and R18 (when
present) each represent n-butyl or n-pentyl.
In an especially preferred embodiment each R1 to R18 and
R31 to R42 group (when present) represents the same
substituent as defined herein. Preferably, each R1 to R18
and R31 to R42 group represents the same Ci to Ce alkyl
group, particularly non-substituted Ci-Ce alkyl, such as
methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl,
tert-butyl, pentyl, hexyl and cyclohexyl, or
trifluoromethyl. Most preferably, each R1 to R18 and R31 to
R42 group represents non-substituted Ci-Ce alkyl,
particularly methyl.
The term adamantyl when used herein means an adamantyl
group which may be bonded to Q1, Q2, Q3, Q4 and Q5,
respectively, in position 1 or 2.
Tricyclo[3.3.1.1.{3,7}]decyl is the systematic name for an
adamantyl group, suitably Q1, Q2, Q3, Q4 and Q5,
respectively, may be bonded to the 1 position or 2
position of one or two tricyclo[3.3.1.1.{3,7}]decyl
groups. Preferably, Q1 and Q2, and Q3, Q4 and Q5, when
present, is bonded to a tertiary carbon of one or more
adamantyl groups. Suitably, when the adamantyl group
represents unsubstituted adamantyl, Q1 and Q2, and Q3, Q4
and Q5 when present are preferably bonded to the 1
position of one or more tricyclo[3.3.1.1(3, 7} ] decyl groups
i.e. the carbon atom of the adamantyl group bears no
hydrogen atom.
The adamantyl group may optionally compri.se, besides
hydrogen atoms, one or more substituents selected from
lower alkyl, -OR19, -OC(0)R20, halo, nitro, -C(O)R21,
-C(0)OR22, cyano, aryl, -N(R23)R24, -C (O)N (R25)R26,
-C(S) (R27)R28, -CF3, -P(R56)R57, -PO(R58) (R59), -P03H2,
-PO(OR60) (OR61), or -S03R62, wherein R19, R20, IR21, R22, R23,
R24, R25, R26, R27, R28, lower alkyl, cyano and aryl are as
defined herein and R56 to R62 each independently represent
hydrogen, lower alkyl, aryl or Het.
Suitably, when the adamantyl group is substituted with one
or more substituents as defined above, highily preferred
substituents include unsubstituted Ci to C8 al.kyl; -OR19, -
OC(0)R20, phenyl, -C{0)OR22, fluoro, -S03K , -N(R23)R24,
-P(R56)R57, -C(0)N(R25)R26 and -PO(R58) (R59) , -CF3, wherein R19
represents hydrogen, unsubstituted Ci-C8 alk^l or phenyl,
R20, R22, R23, R24, R25, R26 each independently represent
hydrogen or unsubstituted Ci-C8 alkyl, R56 to R53, R56 each
independently represent unsubstituted Ci-C8 alkyl or
phenyl.
Suitably, the adamantyl group may comprise, besides
hydrogen atoms, up to' 10 substituents as defined above,
preferably up to 5 substituents as defined above, more
preferably up to 3 substituents as de fined above.
Suitably, when the adamantyl group compri_ses, besides
hydrogen atoms, one or more substituents as defined
herein, preferably each substituent is identical.
Preferred substituents are unsubstituted Cj—C8 alkyl and
trifluoromethyl, particularly unsubstituted- Ci-C8 alkyl
such as methyl. A highly preferred adamantyl group
comprises hydrogen atoms only i.e. the adamantyl group is
not substituted.
Preferably, when more than one adamantyl group is present
i.i a compound of formula III, each adamantyl group is
identical.
By the term 2-phospha-tricyclo[3.3.1.1. {3, 7}]decyl group
we mean a 2-phospha-adamantyl group formed by the
combination of X1 and X2 together with Q2 to which they are
attached, a 2-phospha-adamantyl group formed by the
combination of X3 and X4 together with Q1 to which they are
attached, a 2-phospha-adamantyl group formed by the
combination of X5 and X6 together with Q3 to which they are
attached, a 2-phospha-adamantyl group formed by the
combination of X7 and X8 together with Q4 to which they are
attached and a 2-phospha-adamantyl group formed by the
combination of X9 and X10 together with Q5 to which they
are attached, wherein Q1, Q2, Q3, Q4 and Q5 is in the 2-
position of the adamantyl group of which it forms an
integral part and each of Q1, Q2, Q3, Q4 and Q5 represents
phosphorus.
The 2-phospha-tricyclo[3.3.1.1.{3,7}]decyl group (referred
to as 2-phospha-adamantyl group herein) may optionally
comprise, beside hydrogen atoms, one or more substituents.
Suitable substituents include those substituents as
defined herein in. respect of the adamantyl group. Highly
preferred substituents include lower alkyl, particularly
unsubstituted CI-CB alkyl, especially methyl,
trifluoromethyl, -OR19 wherein R19 is as defined herein
particularly unsubstituted Ci-Cg alkyl or aryl, and 4-
dodecylphenyl. When the 2-phospha-adamantyl group includes
more than one substituent, preferably each substituent is
identical.
Preferably, the 2-phospha-adamantyl group is substituted
on one or more of the 1, 3, 5 or 7 positions with a
substituent as defined herein. More preferably, the 2-
phospha-adamantyl group is substituted on each of the 1, 3
and 5 positions. Suitably, such an arrangement means the
phosphorous atom of the 2-phospha-adamantyl group is
bonded to carbon atoms in the adamantyl skeleton having no
hydrogen atoms. Most preferably, the 2-phospha-adamantyl
group is substituted on each of the 1, 3, 5 and 7
positions. When the 2-phospha-adamantyl group includes
more than 1 substituent preferably each substituent is
identical. Especially preferred substituents are
unsubstituted Ci-C8 alkyl and trifluoromethyl,
particularly unsubstituted Ci-C8 alkyl such as methyl.
Preferably, the 2-phospha-adamantyl group includes
additional heteroatoms, other than the 2-phosphorous atom,
in the 2-phospha-adamantyl skeleton. Suitable additional
heteroatoms include oxygen and sulphur atoms, especially
oxygen atoms. More preferably, the 2-phospha-adamantyl
group includes one or more additional heteroatoms in the
6, 9 and 10 positions. Even more preferably, the 2-
phospha-adamantyl group includes an additional heteroatom
in each of the 6, 9 and 10 positions. Most preferably,
when the 2-phospha-adamantyl group includes two or more
additional heteroatoms in the 2-phospha-adamantyl
skeleton, each of the additional heteroatoms are
identical. An especially preferred 2-phospha-adamantyl
group, which may optionally be substituted with one or
more substituents as defined herein, includes an oxygen
atom in each of the 6, 9 and 10 positions of the 2-
phospha-adamantyl skeleton.
Highly preferred 2-phospha-adamantyl groups as defined
herein include 2-phospha-l,3,5,7-tetramethyl-6,9,10-
trioxadamantyl group, 2-phospha-l,3, 5-trimethyl-6,9,10-
trioxadamantyl group, 2-phospha-l,3,5,7-
tetra(trifluoromethyl)-6,9,10-trioxadamantyl group, and 2-
phospha-1,3,5-tri(trifluoromethyl)-6,9,10-trioxadamantyl
group. Most preferably, the 2-phospha-adamantyl is
selected from 2-phospha-l,3,5,7-tetramethyl-6,9,10-
trioxadamantyl group or 2-phospa-l,3,5,-trimethyl-6,9,10-
trioxadamantyl group.
Preferably, when more than one 2-phospha-adamantyl group
is present in a compound of formula III, each 2-phosphaadamantyl
group is identical.
The above definition of the term M2-phosphatricyclo[
3.3.1.1.{3,7}]decyl group" applies equally to the
group when it is present in formula I but wherein Xn in
formula III, i.e. X1, X2, X3...X10, is denoted CRxRyRz, i.e.
CR^R3, . . .CR16R17R1B, in formula I.
The term congressyl when used herein means a congressyl
group (also known as diamantyl group) which may be bonded
to Q1, Q2, Q3, Q4 and Q5 respectively. Preferably, Q1 and
Q2, and Q3, Q4 and Qs, when present, are bonded to one of
the tertiary carbon atoms of the congressyl groups.
Suitably, when the congressyl group is unsubstituted, Q1
and Q2, and Q3, Q4 and Q5 when present, are preferably
bonded to the 1-position of one or more congressyl groups.
•35
The congressyl group may optionally comprise, beside
hydrogen atoms, one or more substituents. Suitable
substituents include those substituents as defined herein
in respect of the adamantyl group. Highly preferred
substituents include unsubstituted Ci-C6 alkyl groups,
particularly methyl, and trifluoromethyl. Most preferably,
the congressyl group is unsubstituted and comprises
hydrogen atoms only.
Preferably, when more than one congressyl group is present
in a compound of formula III, each congressyl group is
identical.
Preferably, where one or more ring systems of formula
Ilia, Illb, IIIc, Hid or Hie are present in a compound
of formula III, R50 to R53 each independently represent
lower alkyl, aryl or Het, which groups are optionally
substituted and/or terminated as defined herein. Such an
arrangement means Q2, Q1, Q3, Q4 and Q5 of the ring system
of formula Ilia to Hie, respectively, is not bonded to a
carbon atom bearing a hydrogen atom. Even more preferably,
R50 to R53 each independently represent optionally
substituted C1-C6 alkyl, preferably non-substituted Ci-C6
alkyl, phenyl optionally substituted with non-substituted
Ci-Ce alkyl or OR19 where R19 represents non-substituted Ci-
C6 alkyl, or trif luoromethyl. Even more preferably R50 to
R53 each represent the same group as defined herein,
particularly non-substituted Ci-C6 alkyl, especially
methyl.
Preferably, where one or more ring system of formula Ilia
to Hie are present in a compound of formula III, R49 and
3-6
R54 each independently represent optionally substituted Ca-
Ce alky!, preferably non-substituted Ci-Ce alkyl, phenyl
optionally substituted with non-substituted Ci-Ce alkyl or
OR19 where R19 represents non-substituted Ci-C6 alkyl,
trifluoromethyl or hydrogen. More preferably, R49 and R54
x:epresent the same group as defined herein, especially
hydrogen.
Preferably, where one or more ring systems of formula Ilia
to Ille are present in a compound of formula III, Y1 to Y5
are identical. Most preferably, each of Y1 to Y5
represents oxygen. Preferably, where more than one .ring
system of formula Ilia to Ille is present in a compound of
formula III, each such ring system is identical.
Preferred embodiments of the present invention include
those wherein:
X1 represents CR1(R2)(R3 ) , X2 represents CR4(R5){R6 ) , X3
represents CR7(R8) (R9) and X4 represents CR10(Rn) (R12);
X1 represents CR1(R2)(R3 ) , X2 represents adamantyl, X3
represents CR7(R8) (R9) and X4 represents adamantyl;
X1 represents CR1(R2)(R3 ) , X2 represents congressyl, X3
represents CR7(R8) (R9) and X4 represents congressyl;
X1 represents CR1(R2 ) ( R 3 ) , X2 represents CR4 ( R 5 ) ( R 6 ) , and X3
and X4 together with Q1 to which they are attached form a
ring system of formula Illb or a 2-phospha-adamantyl
group;
X1 represents CR1(R2)(R3), X2 represents adamantyl, X3 and
X4 together with Q1 to which they are attached form a ring
system of formula Illb or a 2-phospha-adamantyl group;
X1 represents CR1(R2)(R3), X2 represents congressyl, X3 and
X4 together with Q1 to which they are attached form a ring
system of formula Ilib or a 2-phospha-adamantyl group;
X1 to X4 each independently represent adamantyl;
X1 to X4 each independently represent congressyl;
X1 and X2 each independently represent adamantyl and X3 and
X4 each independently represent congressyl;
X1 and X3 independently represent adamantyl and X2 and X4
independently represent congressyl;
X1 and X2 independently represent adamantyl, X3 represents
CR7(R8) (R9) and X4 represents CR10(RU) (R12);
X1 and X2 independently represent congressyl, X3 represents
CR7(R8) (R9) and X4 represents CR10(RU) (R12) ;
X1 and X2 independently represent adamantyl, and X3 and X4
together with Q1 to which they are attached form a ring
system of formula Illb or a 2-phospha-adamantyl group;
X1 and X2 independently represent congressyl, and X3 and X4
together with Q1 to which they are attached form a ring
system of formula Illb or a 2-phospha-adamantyl group;
X1 and X2 together with Q2 to which they are attached form
a ring system of formula Ilia, and X3 and X4 together with
Q1 to which they are attached form a ring system of
formula Illb;
X1 and X2 together with Q2 to which they are attached form
a 2-phospha-adamantyl group, and X3 and X4 together with Q1
to which they are attached form a 2-phospha-adamantyl
group;
Highly preferred embodiments of the present invention
include those wherein:
X1 represents CR1(R2)(R3), X2 represents CR4(R5)(R6), X3
represents CR7(R8)(R9) and X4 represents CR10 (R11) (R12) ;
X1 represents CR1(R2)(R3), X2 represents adamantyl, X3
represents CR7(R8) (R9) and X4 represents adamantyl;
X1 represents CR1(R2)(R3), X2 represents congressyl, X3
represents CR7(R8)(R9) and X4 represents congressyl;
X1 to X4 each independently represent adamantyl;
X1 to X4 each independently represent congressyl;
X1 and X2 together with Q2 to which they are attached form
a ring system of formula Ilia, and X3 and X4 together with
Q1 to which they are attached form a ring system of
formula Illb;
X1 and X2 together with Q2 to which they are attached form
a 2-phospha-adamantyl group, and X3 and X4 together with Q1
to which they are attached form a 2-phospha-adamantyl
group;
Preferably in a compound of formula III, X1 is identical
to X3 and X2 is identical to X4. More preferably, X1 is
identical to X3 and X5, X7 and X9 when present, and X2 is
identical to X4 and X6, X8 and X10 when present. Even more
preferably, X1 to X4 are identical. Most preferably, X1 to
X4 are identical to each of X6 to X10 when present.
Preferably, in the compound of formula III, X1 and X2
represent identical substituents, X3 and X4 represent
identical substituents, Xs and X6 (when present) represent
identical substituents, X7 and X8 (when present) represent
identical substituents, and X9 and X10 (when present)
represent identical substituents.
Preferably, in a compound of formula III, K1 represents -
Aa-Q3(X5)X6, hydrogen, lower alkyl, -CF3, phenyl or lower
alkyl phenyl. More preferably, K1 represents -A3-Q3 (X5)X6,
hydrogen, unsubstituted Ci-Ce alkyl, unsubstituted phenyl,
trifluoromethyl or Ci-C6 alkyl phenyl.
In a particular preferred embodiment K1 in a compound of
formula III represents hydrogen.
In an alternative embodiment where K1 does not represent
hydrogen, K1 represents -A3-Q3(X5)X6. Preferably, X5 is
identical to X3 or X1, and X6 is identical to X2 or X4.
More preferably, X5 is identical to both X3 and X1, and X6
is identical to both X2 and X4. Even more preferably, -Aa-
Q3(X5)X6 is identical to either -A1-Q2(X1)X2 or -A2-Q1 (X3)X4.
Mo
i-;ost preferably, -A3-Q3(X5)X6 is identical to both -AIQ2(
XX)X2 and -Aa-Q1 (X3)X4.
Most preferably, K1 represents hydrogen in a compound of
formula III.
Preferably, in the compound of formula III, D1 represents
-Ai-Q4 (X7)X8, hydrogen, lower alkyl, CF3, phenyl or lower
alkylphenyl, and E1 represents -A5-Q5 (X9)X10, hydrogen,
lower al'cyl, CF3, phenyl or lower alkylphenyl, or D1 and E1
together with the carbons of the cyclopentadienyl ring to
which they are attached form an optionally substituted
phenyl ring. More preferably, D1 represents -A4-Q4(X7)X8,
hydrogen, phenyl, Ci-C6 axkylphenyl, unsubstituted Ci-C6
alkyl, such as methyl, ethyl, prOpyl, butyl, pentyl and
hexyl, or CF3; E1 represents -As-Q5(X9)X10, hydrogen,
phenyl, Ci-Ce alkylphenyl, unsubstituted Ci-Ce alkyl such
as methyl, ethyl, propyl, butyl, pentyl and hexyl, or -
CF3; or both D1 and E1 together with the carbon atoms of
the cyclopentadienyl ring to which they are attached form
a phenyl ring which is optionally substituted with one or
more groups selected from phenyl, Ci-C6 alkylphenyl,
unsubstituted Ci-C6 alkyl or -CF3.
Suitably, when D1 and E1 together with the carbon atoms of
the cyclopentadienyl ring to which they are attached form
an optionally substituted phenyl ring, the metal M or
cation thereof is attached to an indenyl ring system.
In a particular preferred embodiment, D1 in a compound of
formula III, represents hydrogen.
In an alternative embodiment where D1 does not represent
hydrogen, D1 represents -A4-Q4 (X7)X8. Preferably X8 is
identical to X4 or X2, and X7 is identical to X1 or X3.
More preferably, X8 is identical to both X4 and X2, and X7
is identical to X1 and X3. Even more preferably, -A4-
Q4(X7)X8 is identical to either -Ai-Q2(X1)X2 or -A2-Ql (X3)X4.
Most preferably, -A Q1(X3)X4, and -A3-Q3(X5)X6 if present.
In a particular preferred embodiment, E1 in a compound of
formula III represents hydrogen.
In an alternative embodiment where E1 does not represent
hydrogen, E1 represents -A5-Q5 (X9)X10. Preferably X10 is
identical to X4 or X2, and X9 is identical to X1 or X3.
More preferably, X10 is identical to both X4 and X2, and X9
is identical to X1 and X3. Even more preferably, -A5-
Qs(x9)xio is identical to either -Ai-Q2(Xx)X2 or -Aa-Q1 (X3)X4.
Most preferably, -A5-Q5 (X9)X10 is identical to both -Ar-
Q^X^X2 and -A2-Q1(X3)X4, and -A3-Q3(X5)X6 and -A4-Q4(X7)X8 if
present.
Preferably, in the compound of formula III, when D1 and E1
together with the carbon atoms of the cyclopentadienyl
ring to which they are attached do not form an optionally
substituted phenyl ring, each of K1, D1 and E1 represent an
identical substituent.
In an alternative preferred embodiment, D1 and E1 together
with the carbons of the cyclopentadienyl ring to which
they are attached form an unsubstituted phenyl ring.
Highly preferred embodiments of compounds of formula III
include those wherein:
K1, D1 and E1 are identical substituents as defined herein,
particularly where K1, D1 and E1 represent hydrogen;
K1 represents hydrogen, and D1 and E1 together with the
carbons of the cyclopentadienyl ring to which they are
attached form an unsubstituted phenyl ring;
K1 represents -A3-Q3(X5)X6 as defined herein and both D1 and
E1 represent H;
K1 represents -A3-Q3(X5)X6 as defined herein and D1 and E1
together with the carbon atoms of the cyclopentadienyl
ring to which they are attached form an unsubstituted
phenyl ring;
K1 represents -A3-Q3(X5) X6, D1 represents -A«-Q4(X7)X8 and E1
represents -A5-QS (X9)X10.
Especially preferred compounds of formula III include
those where both D1 and E1 represent hydrogen or D1 and E1
together with the carbon atoms of the cyclopentadienyl
ring to which they are attached form an unsubstituted
phenyl ring, particularly those compounds where both D1
and E1 represent hydrogen.
Preferably, in the compound of formula III, AI and A2, and
As, Aj and A5 (when present), each independently represent
Ci to Ce alkylene which is optionally substituted as
defined herein, for example with lower alkyl groups.
Suitably, AX and A2, and A3, A4 and AS (when present) may
include a chiral carbon atom. Preferably, the lower
alkylene groups which AI to AS may represent are nonsubstituted.
A particular preferred lower alkylene, which
AI to As may independently represent, is -CH2- or -C2H4-.
Most preferably, each of AI and A2, and A3, A4 and A5 (when
present), represent the same lower alkylene as defined
herein, particularly -CH2-.
In the compound of formula III, preferably each Q1 and Q2,
and Q3, Q4 and Q5 (when present) are the same. Most
preferably, each Q1 and Q2, and Q3, Q4 and Q5 (when
present), represents phosphorus.
It will be appreciated by those skilled in the art that
the compounds of formula III may function as ligands that
coordinate with the Group VIB or Group VIIIB metal or
compound thereof in the formation of the catalyst system
of the invention. Typically, the Group VIB or Group VIIIB
metal or compound thereof coordinates to the one or more
phosphorus, arsenic and/or.antimony atoms of the compound
of formula III. It will be appreciated that the compounds
of formula III may be referred to broadly as
"metal locenes".
Suitably, when n = 1 and LI represents an optionally
substituted cyclopentadienyl or indenyl group, the
compounds of formula III may contain either two
cyclopentadienyl rings, two indenyl rings or one indenyl
and one cyclopentadienyl ring (each of which ring systems
may optionally be substituted as described herein). Such
compounds may be referred to as "sandwich compounds" as
the metal M or metal cation thereof is sandwiched by the
two ring systems. The respective cyclopentadienyl and/or
indenyl ring systems may be substantially coplanar with
respect to each other or they may be tilted with respect
to each other (commonly referred to as bent metallocenes) .
Alternatively, when n = 1 and LI represents aryl, the
compounds of the invention may contain either one
cyclopentadienyl or one indenyl ring (each of which ring
systems may optionally be substituted as described herein)
and one aryl ring which is optionally substituted as
defined herein. Suitably, when n = 1 and LI represents
aryl then the metal M of the compounds of formula III as
defined herein is typically in the form of the metal
cation.
In a particularly preferred embodiment of the present
invention, in a compound of formula III, n = 1, LI is as
defined herein and m = 0.
Preferably, when n - 1 in the compound of formula III, LI
represents cyclopentadienyl, indenyl or aryl ring each of
which rings are optionally substituted by one or more
substituents selected from hydrogen, lower alkyl, halo,
cyano, nitro, -OR19, -OC(0)R20, -C(O)R21, -C(0)OR22,
-N(R23)R24, -C(0)N(R25)R26, -C (S) (R27) R28 -SR29, -C (0) SR30,
-CFa or ferrocenyl (by which we mean the cyclopentadienyl,
indenyl or aryl ring which LI may represent is bonded
directly to the cyclopentadienyl ring of the ferrocenyl
group), wherein R19 to R30 is as defined herein. More
preferably, if the cyclopentadienyl, indenyl or aryl ring
which LI may represent is substituted it is preferably
substituted with one or more substituents selected from
unsubstituted Ci-C6 alkyl, halo, cyano, -OR19, -OC(0)R20,
-C(0)R21, -C(0)OR22, -N(R23)R24 where R19, R20, R21, R22, R23
and R24 each independently represent hydrogen or Ci-Ce
alkyl. Even more preferably, if the cyclopentadienyl,
indenyl or aryl ring which LI may represent is
substituted, it is preferably substituted with one or more
substituents selected from unsubstituted Ci-Ce alkyl.
Preferably, when n = 1, LI represents cyclopentadienyl,
indenyl, phenyl or napthyl optionally substituted as
defined herein. Preferably, the cyclopentadienyl, indenyl,
phenyl or napthyl groups are unsubstituted. More
preferably, LI represents cyclopentadienyl, indenyl or
phenyl, each of which rings are unsubstituted. Most
preferably, LI represents unsubstituted cyclopentadienyl.
Alternatively, when n = 0, the compounds of the invention
contain only one cyclopentadienyl or indenyl ring (each of
which ring systems may optionally be substituted as
described herein) . Such compounds may be referred to as
"half sandwich compounds". Preferably, when n = 0 then m
represents 1 to 5 so that the metal M of the compounds of
formula III has an 18 electron count. In other words, when
metal M of the compounds of formula III is iron, the total
number of electrons contributed by the ligands La is
typically five.
In a particularly preferred alternative embodiment of the
present invention, in a compound of formula III, n = 0, La
is as defined herein and m = 3 or 4, particularly 3.
Preferably, when n is equal to zero and m is not equal to
zero in a compound of formula III, L2 represents one or
more ligands each of which are independently selected from
lower alkyl, halo, -CO, -P (R43) (R44) R45 or -N (R46) (R47) R48.
More preferably, L2 represents one or more ligands each of
which are independently selected from unsubstituted Ci to
C4 alkyl, halo, particularly chloro, -CO, -P (R43) (R44)R45 or
-N(R46) (R47)R48, wherein R43 to R48 are independently
selected from hydrogen, unsubstituted Ci to Ce alkyl or
aryl, such as phenyl.
Suitably, the metal M or metal cation thereof in the
compounds of formula III is typically bonded to the
cyclopentadienyl ring(s), the cyclopentadienyl moiety of
the indenyl ring(s) if present, the aryl ring if present,
and/or the ligands L2 if present. Typically, the
cyclopentadienyl ring or the cyclopentadienyl moiety of
the indenyl ring exhibits a pentahapto bonding mode with
the metal; however other bonding modes between the
cyclopentadienyl ring or cyclopentadienyl moiety of the
indenyl ring and the metal, such as trihapto coordination,
are also embraced by the scope of the present invention.
Most preferably, in a compound of formula III, n = l, m =
0 and LI is defined herein, particularly unsubstituted
cyclopentadienyl.
Preferably M represents a Group VIB or VIIIB metal. In
other words the total electron count for the metal M is
18.
Preferably, in the compound of formula III, M represents
Cr, Mo, Fe, Co or Ru, or a metal cation thereof. Even more
preferably, M represents Cr, Fe, Co or Ru or a metal
cation thereof. Most preferably, M is selected from a
Group VIIIB metal or metal cation thereof. An especially
preferred Group VIIIB metal is Fe. Although the metal M as
Mldefined
herein may be in a cationic form, preferably ,it
carries essentially no residual charge due to coordination
with LI and/or L2 as defined herein.
Especially preferred compounds of formula III include
those wherein:
(1) X1 represents CR1(R2)(R3), X2 represents CR4(R5)(R6),
X3 represents CR7(R8)(R9), X4 represents CR10 (R11) (R12),
wherein each of R1 to R12 independently represents
unsubstituted Ci-C6 alkyl or trifluoromethyl,
particularly where each of R1 to R12 is identical,
especially where each of R1 to R12 represents
unsubstituted Ci-C6 alkyl, particularly methyl;
AI and AZ are the same and represent -CH2-;
K1, D1 and E1 are the same and represent hydrogen or
unsubstituted Ci-Ce alkyl, particularly hydrogen;
Q1 and Q2 both represent phosphorus;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
(2) X1 represents CR1(R2)(R3), X2 represents CR4{R5)(R6),
X3 represents CR7(R8)(R9), X4 represents CR10 (R11) (R12);
K1 represents -CH2-Q3 (Xs) X6 wherein X5 represents
CR13(R14) (R15) and X6 represents CR16(R17) (R18) ;
each of R1 to R18 independently represent
unsubstituted Ci-Ce alkyl or trifluoromethyl,
particularly where each of R1 to R18 is identical,
especially where each of R1 to R18 represents
unsubstituted Ci-Ce alkyl, particularly methyl;
AI and A2 are the same and represent -CH2-;
Q1, Q2 and Q3 each represent phosphorus;
D1 and E1 are the same and represent hydrogen or
unsubstituted Ci-Ce alkyl, particularly hydrogen;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
(3) X1 represents CR^R2}^3}, X2 represents CR4 (R5) (R6),
X3 represents CR7(R8)(R9), X4 represents CR10^11) (R12) ;
K1 represents -CH2-Q3(X5) X€ wherein X5 represents
CR13(R14) (R15) and X6 represents CR16(R17) (R18);
each of R1 to R18 independently represent
unsubstituted Ci-Ce alkyl or trifluoromethyl,
particularly where each of R1 to R18 is identical,
especially where each of R1 to R18 represents
unsubstituted Ci-Ce alkyl, particularly methyl;
AI and Aa are the same and represent -CH2-;
Q1, Q2 and Q3 each represent phosphorus;
D1 and E1 together with the carbon atoms of the
cyclopentadienyl ring to which they are attached
form an unsubstituted phenyl ring;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
(4) X1 represents CR1(R2)(R3), X2 represents CR4(R5)(R6),
X3 represents CR7(RB)(R9), X4 represents CR10(R11) (R12) ,
wherein each of R1 to R12 independently represent
unsubstituted Ci-C6 alkyl or trifluoromethyl,
particularly where each of R1 to R12 is identical,
especially where each of R1 to R12 represents
unsubstituted Ci~C6 alkyl, particularly methyl;
AI and AZ are the same and represent -CH2-;
Q1 and Q2 both represent phosphorus;
K1 represents hydrogen or Ci-Ce alkyl, particularly
hydrogen;
D1 and E1 together with the carbon atoms of the
cyclopentadienyl ring to which they are attached
form an unsubstituted phenyl ring;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
(5) X1 represents CR1(R2)(R3), X2 represents CR4(R5)(R6 ) ,
X3 represents CR7(R8)(R9 ) , X4 represents CR10(Rn) (R12) ;
E1 represents -CH2-Q5 (X9)X10 wherein X9 represents
CR37(R3B) (R39) and X10 represents CR40(R41) (R42);
each of R1 to R12 and R37 to R42 independently
represent unsubstituted Ci-Ce alkyl or
trifluoromethyl, particularly where each of R1 to R12
and R37 to R42 is identical, especially where each of
R1 to R12 and R37 to R42 represents unsubstituted Ci-Ce
alkyl, particularly methyl;
AI and A2 are the same and represent -CHa-;
Q1, Q2 and Q5 each represent phosphorus;
D1 and K1 are the same and represent hydrogen or
unsubstituted Ci-Ce alkyl, particularly hydrogen;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
(6) X1 represents CR1(R2)(R3 ) , X2 represents CR4 ( R 5 ) ( R 6 ) ,
X3 represents CR7(R8) (R9 ) , X4 represents CR10(RU) (R12);
K1 represents -CH2-Q3 (X5)X6 wherein X5 represents
CR13(R14) (R15) and X6 represents CR16(R17) (R18);
D1 represents -CH2-Q4 (X7)X8 wherein X7 represents
CR31(R32) (R33) and X8 represents CR34(R35) (R36);
E1 represents -CH2-Q5 (X9)X10 wherein X9 represents
CR37(R38) (R39) and X10 represents CR40(R41) (R42) ;
each of R1 to R18 and R31 to R42 independently
represent unsubstituted Ci-Ce alkyl or
trifluoromethyl, particularly where each of R1 to R18
and R31 to R42 is identical, especially where each
of R1 to R18 and R31 to R42 represents unsubstituted
Ci-C6 alkyl, particularly methyl;
AI and Aa are the same and represent -CH2-;
Q1r Q2/ Q3
Q4 and Q5 each represent phosphorus
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyL, and m =
0.
(7) X1, X2, X3 and X4 independently represent adamantyl,
especially where X1 to X4 represent the same
adamantyl group;
AI and Aa are the same and represent -CHa-;
K1, D1 and E1 are the same and represent hydrogen or
unsubstituted Ci-C6 alkyl, particularly hydrogen;
Q1 and Q2 both represent phosphorus;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
(8) X1, X2, X3 and X4 independently represent adamantyl,
especially where X1 to X4 represent the same
adamantyl group;
K1 represents -CH2-Q3 (X5)X6 wherein X5 and X6
independently represent adamantyl, especially where
X1 to X6 represent the same adamantyl group;
AI and Aa are the same and represent -CHa-;
Q1, Q2 and Q3 each represent phosphorus;
D1 and E1 are the same and represent hydrogen or
unsubstituted Ci-Cg alkyl, particularly hydrogen;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
(9) X1, X2, X3 and X4 independently represent adamantyl,
especially where X1 to X4 represent the same
adamantyl group;
K1 represents -CH2-Q3(X5)X6 wherein X5 and X6
independently represent adamantyl, especially where
X1 to X6 represent the same adamantyl group;
AI and Aa are the same and represent -CHa-;
Q1, Q2 and Q3 each represent phosphorus;
D1 and E1 together with the carbon atoms of the
cyclopentadienyl ring to which they are attached
form an unsubstituted phenyl ring;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
(10) X1, X2, X3 and X4 independently represent adamantyl,
especially where X1 to X4 represent the same
adamantyl group;
Ai and A2 are the same and rrepresent -CH2-;
Q1 and Q2 both represent phosphorus;
K1 represents hydrogen or xinsubstituted Ci-Ce alkyl,
particularly hydrogen;
D1 and E1 together with -the carbon atoms of the
cyclopentadienyl ring to which they are attached
form an unsubstituted phenyl ring;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
(11) X1, X2, X3 and X4 independently represent adamantyl;
K1 represents -CH2-Q3 (X5) IX6 wherein X5 and X6
independently represent adamantyl;
D1 represents -CH2-Q4 (X7) IX8 wherein X7 and X8
independently represents adamantyl;
E1 represents -CH2-Q5 (X9)X10 wherein X9 and X10
independently represents adamantyl, especially where
X1 to X10 represent the same adamantyl group;
AI and A2 are the same and rrepresent -CH2-;
Q1/ Q2/ Q3f Q4 and Q5 each represent phosphorus;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
(12) X1 and X2 together with Q2 to which they are attached
represents 2-phospha-adaman-tyl;
X3 and X4 together with Q1 to which they are attached
represents 2-phospha-adamantyl;
AI and A2 are the same and represent -CH2-;
K1, D1 and E1 are the same and represent hydrogen or
unsubstituted Ci-C6 alkyl, particularly hydrogen;
Q1 and Q2 both represent phosphorus;
M represents Fe;
n = 1 and LI represents cyclopentadienyl/
particularly unsubstituted cyclopentadienyl, and m =
0.
(13) X1 and X2 together with Q2 to which they are attached
represents 2-phospha-adamantyl;
X3 and X4 together with Q1 to which they are attached
represents 2-phospha-adamantyl;
K1 represents -CH2-Q3(X5)X6 wherein X5 and X6 together
with Q3 to which they are attached represents 2-
phospha-adamantyl;
AI and AZ are the same and represent -CHa-;
Q1, Q2 and Q3 each represent phosphorus;
D1 and E1 are the same and represent hydrogen or
unsubstituted Ci-Ce alkyl, particularly hydrogen;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
(14) X1 and X2 together with Q2 to which they are attached
represents 2-phospha-adamantyl;
X3 and X4 together with Q1 to which they are attached
represents 2-phospha-adamantyl;
K1 represents -CH2-Q3(X5)X6 wherein X5 and X6 together
with Q3 to which they are attached represents 2--
phospha-adamantyl ;
AI and A2 are the same and represent -CH2-;
Q1, Q2 and Q3 each represent phosphorus;
D1 and E1 together with the carbon atoms of the
cyclopentadienyl ring to which they are attached
form an unsubstituted phenyl ring;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
(15) X1 and X2 together with Q2 to which they are attached
represents 2-phospha-adamantyl;
X3 and X4 together with Q1 to which they are attached
represents 2-phospha-adamantyl;
AI and A2 are the same and represent -CHa-;
Q1 and Q2 both represent phosphorus;
K1 represents hydrogen or unsubstituted Ci-Ce alkyl,
particularly hydrogen;
D1 and E1 together with the carbon atoms of the
cyclopentadienyl ring to which they are attached
form an unsubstituted phenyl ring;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
(16) X1 and X2 together with Q2 to which they are attached
represents 2-phospha-adamantyl;
X3 and X4 together with Q1 to which they are attached
represents 2-phospha-adamantyl;
K1 represents -CH2-Q3(X5)X6 wherein X5 and X6 together
with Q3 to which they are attached represents 2--
phospha-adamantyl ;
D1 represents -CH2-Q4 (X7)X8 wherein X7 and X8 together
with Q4 to which they are attached represents 2-
phospha-adamantyl;
E1 represents -CH2-Q5 (X9)X10 wherein X9 and X10
together with Q5 to which they are attached
represents 2-phospha-adamantyl;
AI and Aj are the same and represent -CHa-;
Q1* Q2/ Q3/ Q4 and Q5 each represent phosphorus
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
(17) X1 and X2 together with Q2 to which they are attached
form a ring system of formula Ilia, X3 and X4
together with Q1 to which they are attached form a
ring system of formula Illb, wherein Y1 and Y2 both
represent oxygen, R50 to R53 are independently
selected from unsubstituted Ci-Cg alkyl or CFa, and
R49 and R54 represent hydrogen;
AI and AZ are the same and represent -CH2-;
K1, D1 and E1 are the same and represent hydrogen or
unsubstituted Ci-Ce alkyl, particularly hydrogen;
Q1 and Q2 both represent phosphorus;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl
(referred to as puc) and m = 0.
(18) X1 and X2 together with Q2 to which they are attached
form a ring system of formula Ilia, X3 and X4
together with Q1 to which they are attached form a
ring system of formula Illb, wherein Y1 and Y2 both
represent oxygen, R50 to R53 are independently
selected from unsubstituted Ci-Ce alkyl or CFa, and
R49 and R54 represent hydrogen;
Kl represents -CH2-Q3(X5)X6 wherein Xs and X6 together
with Q3 to which they are attached form a ring
system of formula IIIc, wherein Y3 represents
oxygen, R50 to R53 are independently selected from
hydrogen, unsubstituted Ca-Ce alkyl or CFa and R49 and
R54 represent hydrogen;
AI and AZ are the same and represent -CH2-;
Q1/ Q2 and Q3 each represent phosphorus;
D1 and E1 are the same, and represent hydrogen or Cj.-
Ce alkyl, particularly hydrogen;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
(19) X1 and X2 together with Q2 to which they are attached
form a ring system of formula Ilia, X3 and X4
together with Q1 to which they are attached form a
ring system of formula Illb, wherein Y1 and Y2 both
represent oxygen, R50 to R53 are independently
selected from unsubstituted Ci-C6 alkyl or CF3, and
R49 and R54 represent hydrogen;
K1 represents -CH2-Q3(X5)X6 wherein X5 and X6 together
with Q3 to which they are attached form a ring
system of formula IIIc, wherein Y3 represents
oxygen, R50 to R53 are independently selected from
unsubstituted Ci-C6 alkyl or CF3, and R49 and R54
represent hydrogen;
AI and A2 are the same and represent -CH2-;
Q1, Q2 and Q3 each represent phosphorus;
D1 and E1 together with the carbon atoms of the
cyclopentadienyl ring to which they are attached
form an unsubstituted phenyl ring;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
(20) X1 and X2 together with Q2 to which they are attached
form a ring system of formula Ilia, X3 and X4
together with Q1 to which they are attached form a
ring system of formula Illb, wherein Y1 and Y2 both
represent oxygen, R50 to R53 are independently
selected from unsubstituted Ci-Ce alkyl or CFa, and
R49 and R54 represent hydrogen;
AI and A2 are the same and represent -CH2-;
Q1 and Q2 both represent phosphorus;
K1 represents hydrogen or unsubstituted Ci-Ce alkyl,
particularly hydrogen;
D1 and E1 together with the carbon atoms of the
cyclopentadienyl ring to which they are attached
form an unsubstituted phenyl ring;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
(21) X1 and X2 together with Q2 to which they are attached
form a ring system of formula Ilia, X3 and X4
together with Q1 to which they are attached form a
ring system of formula Illb, wherein Y1 and Y2 both
represent oxygen, R50 to R53 are independently
selected from unsubstituted Ci-Ce alkyl or CF3, and
R49 and R54 represent hydrogen;
K1 represents -CH2-Q3(X5)X6 wherein X5 and X6 together
with Q3 to which they are attached form a ring
system of formula IIIc, wherein Y3 represents
oxygen, R50 to R53 are independently selected from
unsubstituted Ci-C6 alkyl or CF3f and R49 and R54
represent hydrogen;
D1 represents -CH2-Q4 (X7)X8 wherein X7 and X8 together
with Q4 to which they are attached form a ring
system of formula TIIc, wherein Y3 represents
oxygen, R50 to R53 are independently selected from
unsubstituted Ci-C6 alkyl or CF3/ and R49 and R54
represent hydrogen;
E1 represents -CH2-Q5 (X9)X10 wherein X9 and X10
together with Q5 to which they are attached form a
ring system of formula Hie, wherein Y5 represents
oxygen, and R50 to R53 are independently selected
from unsubstituted Ci-C6 alkyl or CF3, and R49 and R54
represent hydrogen;
AI and AZ are the same and represent -Cfo-;
Q1/ Q2, Q3/ Q4 and Q5 each represent phosphorus;
M represents Fe;
n = 1 and LI represents cyclopentadienyl;
particularly unsubstituted cyclopentadienyl, and m =
0.
(22) X1, X2, X3 and X4 independently represent congressyl,
especially where X1 to X4 represent the same
congressyl group;
AI and A2 are the same and represent -CH2-;
K1, D1 and E1 are the same and represent hydrogen or
unsubstituted Ci-C6 alkyl, particularly hydrogen;
Q1 and Q2 both represent phosphorus;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
23) X1, X2, X3 and X4 independently represent congressyl,
especially where X1 to X4 represent the same
congressyl group;
K1 represents -CH2-Q3(X5)X6 wherein X5 and X6
independently represent congressyl, especially where
X1 to X6 represent the same congressyl group;
AI and A2 are the same and represent -CH2-;
Q1, Q2 and Q3 each represent phosphorus;
D1 and E1 are the same and represent hydrogen or
unsubstituted Ci-Cg alkyl, particularly hydrogen;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
24) X1, X2, X3 and X4 independently represent congressyl,
especially where X1 to X4 represent the same
congressyl group;
K1 represents -CH2-Q3(X5)X6 wherein X5 and X6
independently represent congressyl, especially where
X1 to X6 represent the same congressyl group;
AI and A2 are the same and represent -CH2-;
Q1, Q2 and Q3 each represent phosphorus;
D1 and E1 together with the carbon atoms of the
cyclopentadienyl ring to which they are attached
form an unsubstituted phenyl ring;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
(25) X1, X2, X3 and X4 independently represent congressyl,
especially where X1 to X4 represent the same
congressyl group;
AI and A2 are the same and represent -CHa-;
Q1 and Q2 both represent phosphorus;
K1 represents hydrogen or unsubstituted Ci-Ce alkyl,
particularly hydrogen;
D1 and E1 together with the carbon atoms of the
cyclopentadienyl ring to which they are attached
form an unsubstituted phenyl ring;
M represents Fe;
. n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
(26) X1, X2, X3 and X4 independently represent congressyl;
K1 represents -CH2-Q3(X5) X6 wherein X5 and X6
independently represent congressyl;
D1 represents -CH2-Q4 (X7) X8 wherein X7 and X8
independently represents congressyl;
E1 represents -CH2-Q5(X9)X10 wherein X9 and X10
independently represents congressyl, especially
where X1 to X10 represent the same congressyl group;
AI and A2 are the same and represent -CHa-;
Q1/ Q2/ Q3/ Q4 and Q5 each represent phosphorus;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
(27) X1 and X3 independently represent adamantyl,
especially where X1 and X3 represent the same
adamantyl group;
X2 represents CR4(R5)(R6 ) and X4 represents
CR10(RU) (R12) wherein each of R4, R5, R6, R10, R11 and
R12 independently represent Ci-C6 alkyl or
trifluoromethyl, particularly where each of R4 to R6
and R10 to R12 is identical, especially where each of
R4 to R6 and R10 to R12 represents unsubstituted C^-Ce
alkyl, particularly methyl;
AI and Aa are the same and represent -CH2-;
K1, D1 and E1 are the same and represent hydrogen or
unsubstituted Ci-C6 alkyl, particularly hydrogen;
Q1 and Q2 both represent phosphorus;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m -
0.
(28) X1 and X3 independently represent adamantyl,
especially where X1 and X3 represent the same
adamantyl group;
K1 represents -CH2-Q3 (X5)X6 wherein X5 represents
adamantyl, especially where X1, X3 and X5 represent
the same adamantyl group;
X2 represents CR4 ( R 5 ) ( R 6 ) , X4 represents CR10(Rn) (R12) ,
(Formula Removed)
unsubstituted Ci-Ce alkyl or trifluoromethyl,
particularly where each of R4 to R6, R10 to R12, and
R16 to R18 is identical, especially where each of R4
to R6, R10 to R12 and R16 to R18 represents
unsubstituted Ci-Ce alkyl, particularly methyl;
AI and Aa are the same and represent -CHa-;
Q1, Q2 and Q3 each represent phosphorus;
D1 and E1 are the same and represent hydrogen or
unsubstituted Ci-Ce alkyl, particularly hydrogen;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
(29) X1 and X3 independently represent adamantyl,
especially where X1 and X3 represent the same
adamantyl group;
K1 represents -CH2-Q3(X5)X6 wherein X5 represents
adamantyl, especially where X1, X3 and Xs represent
the same adamantyl group;
X2 represents CR4(R5)(R6), X4 represents CR10(RU) (R12) ,
X6 represents CR16(R17) (R18), wherein each of R4 to R6,
R10 to R12 and R16 to R18 independently represent
unsubstituted Ci-C6 alkyl or trifluoromethyl,
particularly where each of R4 to R6, R10 to R12, and
R16 to R18 is identical, especially where each of R4
to R6, R10 to R12 and R16 to R18 represents
unsubstituted Ci-Cg alkyl, particularly methyl;
AI and A2 are the same and represent -CHa-;
Q1, Q2 and Q3 each represent phosphorus;
D1 and E1 together with the carbon atoms of the
cyclopentadienyl ring to which they are attached
form an unsubstituted phenyl ring;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
(30) X1 and X3 independently represent adamant yl,
especially where X1 and X3 represent the same
adamantyl group;
X2 represents CR4(R5)(R6 ) and X4 represents
CR10(R11) (R12) wherein each of R4, R5, R6, R10, R11 and
R12 independently represent Ci-Ce alkyl or
trifluoromethyl, particularly where each of R4 to R6
and R10 to R12 is identical, especially where each of
R4 to R6 and R10 to R12 represents unsubstituted Ci-C6
alkyl, particularly methyl;
AI and AZ are the same and represent -GHz-;
Q1 and Q2 both represent phosphorus;
K1 represents hydrogen or unsubstituted Ci-Ce alkyl,
particularly hydrogen;
D1 and E1 together with the carbon atoms of the
cyclopentadienyl ring to which they are attached
form an unsubstituted phenyl ring;
M represents Fe;
n = 1 and LI represents cyclopentadienyl,
particularly unsubstituted cyclopentadienyl, and m =
0.
Specific but non-limiting examples of bidentate ligands
within this embodiment include the following: 1,2-bis-
(dimethylaminomethyl)ferrocene, 1,2-bis-
(ditertbutylphosphinomethyl) ferrocene, l-hydroxymethyl-2-
dimethylaminomethylferrocene, 1,2-bis-
(ditertbutylphosphinomethyl) ferrocene, 1-hydroxymethyl2,
3-bis- (dimethylaminomethyl) ferrocene, 1,2,3-tris-
(ditertbutylphosphinomethyl) ferrocene, 1, 2-bis-
(dicyclohexylphosphinomethyl) ferrocene, 1,2-bis- (di-isobutylphosphinomethyl)
ferrocene, 1, 2-bis-
(dlcyclopentylphosphinomethyl) ferrocene, 1, 2-bis-
(diethylphosphinomethyl) ferrocene, 1,2-bis (diis
opropylphosphinomethyl) ferrocene, 1,2-bis-
(dimethylphosphinomethyl) ferrocene, 1,2-bis- (di- (1,3,5,7-
tetramethyl-6, 9,10-trioxa-2-phosphaadamantylraethyl))
ferrocene, 1,2-bis-
(dimethylaminomethyl) ferrocene-bismethyl iodide, 1,2-
bis (dihydroxymethylphosphinomethyl) ferrocene, 1,2-
bis (diphosphinomethyl)ferrocene, l,2-bis-a,a-(P-(2,2,6, 6,-
tetramethylphosphinan-4-one)) dimethyl ferrocene, and 1,2-
bis- (di-1, 3, 5,7-tetramethyl-6, 9,10-trioxa-2-phosphaadamantylmethyl)
)benzene. Nevertheless, the skilled
person in the art would appreciate that other bidentate
ligands can be envisaged without departing from the scope
of the invention.
According to a further aspect, the present invention
provides a catalyst system capable of catalysing the
carbonylation of an ethylenically unsaturated compound,
said system comprising:
a) a metal of Group VIB or Group VII IB or a compound
thereof,
b) a bidentate phosphine, arsine, or stibine ligand,
preferably a bidentate phosphine ligand, and
c) an acid,
wherein said ligand is present in at least a 2:1 molar
excess compared to said metal or said metal in said metal
compound, and that said acid is present in at least a 2:1
molar excess compared to said ligand.
For the avoidance of any doubt, it is hereby stated that
any of the features and embodiments described hereinbefore
are equally applicable to this aspect.
According to a further aspect, the present invention
provides a process for the carbonylation of an
ethylenically unsaturated compound comprising contacting
an ethylenically unsaturated compound with carbon monoxide
and a hydroxyl group containing compound in the presence
of a catalyst system as defined in the present invention,
such as defined in the first aspect of the present
invention. Preferably, the process is a liquid phase
continuous process comprising the step noted above.
Nevertheless, although the process is preferably operated
continuously, batch operation is possible.
According to a yet further aspect, the present invention
provides a process for the carbonylation of an
ethylenically unsaturated compound comprising contacting
an ethylenically unsaturated compound with carbon monoxide
and a hydroxyl group containing compound in the presence
of a catalyst system, said system comprising:
a) a metal of Group VIB or Group VII IB or a compound
thereof,
b) a bidentate phosphine, arsine, or stibine ligand,
preferably a bidentate phosphine ligand, and
c) an acid,
wherein said ligand is present in at least a 2:1 molar
excess compared to said metal or said metal in said metal
compound, and that said acid is present in at least a 2:1
molar excess compared to said ligand.
Suitably, the hydroxyl group containing compound includes
water or an organic molecule having a hydroxyl functional
group. Preferably, the organic molecule having a hydroxyl
functional group may be branched or linear, and comprises
an alkanol, particularly a Ci-Cao alkanol, including aryl
alkanols, which may be optionally substituted with one or
more substituents selected from lower alkyl, aryl, Het,
halo, cyano, nitro, OR19, OC(O)R20, C(0)R21, C(0)OR22,
NR23R24, C(0)NR25R26, C(S)R25R26, SR27 or C(0)SR28 as defined
herein. Highly preferred alkanols are Ci-Ce alkanols such
as methanol, ethanol, propanol, iso-propanol, iso-butanol,
t-butyl alcohol, n-butanol, phenol and chlorocapryl
alcohol. Although the monoalkanols are most preferred,
poly-alkanols r preferably, selected from di-octa ols such
as diols, txiols, tetra-ols and sugars may also be
utilised. Typically, such polyalkanols are selected from
1, 2-ethanediol, 1,3-propanediol, glycerol, 1,2,4
butanetriol, 2-(hydroxymethyl)-1,3-propanediol, 1,2,6
trihydroxyhexane, pentaerythri tol, 1,1,1
tri(hydroxymethyl) ethane, nannose, sorbase, galactose and
other sugars. Preferred sugars include sucrose, fructose
and glucose. Especially preferred alkanols are methanol
and ethanol. The most preferred alkanol is methanol.
The amount of alcohol is not critical. Generally, amounts
are used in excess of the amount of ethylenically
unsaturated compound to be carbonylated. Thus the alcohol
may serve as the reaction solvent as well, although, if
desired, separate solvents may also be used.
It will be appreciated that the end product of the
reaction is determined at least in part by the source of
hydroxyl group containing compound used. If water is used
as the hydroxyl group containing compound then the end
product is the corresponding carboxylic acid, whereas use
of an alkanol produces the corresponding ester.
It will also be appreciated that the process of the
present invention may start with a catalyst system having
components providing molar ratios above or below those
claimed but such ratios will progress to values within
said ranges claimed during the course of the reaction.
It will of course also be appreciated that the levels of
such components present within the catalyst system may
change during the process of the invention as further
amounts off some or all of the components are added to
maintain the usable levels of components within the
catalyst system. Some of the components of the catalyst
system may drop out of the system during the reaction
process and therefore levels may need to be topped-up to
maintain levels within the actual catalyst system.
As stated hereinbefore, it will be appreciated by those
skilled in the art that the phosphines described herein
may function as ligands that coordinate with the Group VIB
or Group VIIIB metal or compound, together with the
present acid, to form a complex. This complex may
represent part of the effective catalyst in the present
invention and hence may represent part of the catalyst
system defined herein.
Thus, in a further aspect, the present invention provides
a complex capable of catalysing the carbonylation of an
ethylenically unsaturated compound, said complex
obtainable by combining:
a) a metal of Group VIB or Group VII IB or a compound
thereof,
b) a bidentate phosphine, arsine, or stibine ligand,
preferably a bidentate phosphine ligand, and
c) an acid,
wherein said ligand is present in at least a 2:1 molar
excess compared to said metal or said metal in said metal
compound, and that said acid is present in at least a 2:1
molar excess compared to said ligand.
In a yet further aspect, the present invention provides a
process for the carbonylation of an ethylenically
unsaturated compound with carbon monoxide and a hydroxyl
group containing compound in the presence of a complex,
said complex as defined above.
In the process according to the present invention, the
carbon monoxide may be used in pure form or diluted with
an inert gas such as nitrogen, carbon dioxide or a noble
gas such as argon. Small amounts of hydrogen, typically
less than 5% by volume, may also be present.
The ratio (volume/volume) of ethylenically unsaturated
compound to hydroxyl group containing compound may vary
between wide limits and suitably lies in the range of
1:0.1 to 1:10, preferably from between 2:1 to 1:2 and up
to a large excess of hydroxyl group containing compounds
when the latter is also the reaction solvent such as up to
a 50:1 excess of hydroxyl group containing compounds.
The mqlar ratio of the ethylenically unsaturated compound
to carbon monoxide is preferably in the range 1:1 to 100:1
more preferably greater than 1:1, even more preferably at
least 3:1, especially from 3:1 to 50:1, and most
preferably in the range from 3:1 to 15:1.
The amount of the catalyst of the invention used in the
carbonylation process of the ethylenically unsaturated
compound is not critical. Good results may be obtained
when, preferably, the amount of Group VIB or VIIIB metal
is in the range 10"7 to 10"1 moles per mole of
ethylenically unsaturated compound, more preferably, 10~6
to 10~2 moles, most preferably 10"5 to 10~2 moles per mole
of ethylenically unsaturated compound. Preferably, the
amount of bidentate compound of formula I or formula III
to unsaturated compound is in the range 10"7 to 10"1, more
preferably, 10~6 to 10"2, most preferably, 10~5 to 10"2
moles per mole of ethylenically unsaturated compound.
Suitably, although non-essential to the invention, the
carbonylation of an ethylenically unsaturated compound as
defined herein may be performed in one or more aprotic
solvents. Suitable solvents include ketones, such as for
example methylbutylketone; ethers, such as for example
anisole (methyl phenyl ether), 2,5,8-trioxanonane
(diglyme), diethyl ether, dimethyl ether, tetrahydrofuran,
diphenylether, diisopropylether and the dimethylether of
di-ethylene-glycol; esters, such as for example
methylacetate, dimethyladipate methyl benzoate, dimethyl
phthalate and butyrolactone; amides, such as for example
dimethylacetamide, N-methylpyrrolidone and dimethyl
formamide; sulfoxides and sulphones, such as for example
dimethylsulphoxide, di-isopropylsulphone, sulfolane
(tetrahydrothiophene-2,2-dioxide), 2-methylsulfolane,
diethyl sulphone, tetrahydrothiophene 1,1-dioxide and 2-
methyl-4-ethylsulfolane; aromatic compounds, including
halo variants of such compounds eg. benzene, toluene,
ethyl benzene o-xylene, m-xylene, p-xylene, chlorobenzene,
o-dichlorobenzene, m-dichlorobenzene: alkanes, including
halo variants of such compounds eg, hexane, heptane,
2,2,3-trimethylpentane, methylene chloride and carbon
tetrachloride; nitriles eg. benzonitrile and acetonitrile.
Very suitable are aprotic solvents having a dielectric
constant that is below a value of 50, more preferably in
the range of 3 to 8, at 298.15 K and 1 x 105Nm"2. In the
present context, the dielectric constant for a given
solvent is used in its normal meaning of representing the
ratio of the capacity of a condenser with that substance
as dielectric to the capacity of the same condenser with a
vacuum for dielectric. Values for the dielectric constants
of common organic liquids can be found in general
reference books, such as the Handbook of Chemistry and
Physics, 76th edition, edited by David R. Lide et al, and
published by CRC press in 1995, and are usually quoted for
a temperature of about 20°C or 25°C, i.e. about 293.15k or
298.15 K, and atmospheric pressure, i.e. about 1 x 105Nm~2,
or can readily be converted to that temperature and
pressure using the conversion factors quoted. If no
literature data for a particular compound is available,
the dielectric constant may be readily measured using
established physico-chemical methods.
For example, the dielectric constant of anisole is 4.3 (at
294.2 K), of diethyl ether is 4.3 (at 293.2 K) , of
sulfolane is 43.4 (at 303.2 K), of methylpentanoate is 5.0
(at 293.2 K), of diphenylether is 3.7 (at 283.2 K), of
dimethyladipate is 6.8 (at 293.2 K), off tetrahydrofuran is
7.5 (at 295.2 K), of methylnonanoate is 3.9 (at 293.2 K) .
A preferred solvent is anisole.
If the hydroxyl group containing compound is an alkanol,
an aprotic solvent will be generated by the reaction as
the ester carbonylation product of the ethylenically
unsaturated compound, carbon monoxide and the alkanol is
an aprotic solvent.
The process may be carried out in an excess of aprotic
solvent, i.e. at a ratio (v/v) of aprotic solvent to
hydroxyl group containing compound of at least 1:1.
Preferably, this ratio ranges from 1:1 to 10:1 and more
preferably from 1:1 to 5:1. Most preferably the ratio
(v/v) ranges from 1.5:1 to 3:1.
Despite the aforegoing it is preferred that the reaction
is carried out in the absence of any external added
aprotic solvent ie. an aprotic solvent not generated by
the reaction itself.
The catalyst compounds of the present invention may act as
a "heterogeneous" catalyst or a "homogeneous" catalyst.
By the term "homogeneous" catalyst we mean a catalyst,
i.e. a compound of the invention, which is not supported
but is simply admixed or formed in-situ with the reactants
of the carbonylation reaction (e.g. the ethylenically
unsaturated compound, the hydroxyl containing compound and
carbon monoxide) , preferably in a suitable solvent as
described herein.
By the term "heterogeneous" talyst we mean a catalyst,
i.e. the compound of the invasion, which is carried on a
support.
Thus according to a further aspect, the present invention
provides a process for the carbonylation of ethylenically
unsaturated compounds as defined herein wherein the
process is carried out with the catalyst comprising a
support, preferably an insoluble support.
Preferably, the support comprises a polymer such as a
polyolefin, polystyrene or polystyrene copolymer such as a
divinylbenzene copolymer or other suitable polymers or
copolymers known to those skilled in the art; a silicon
derivative such as a functionalised silica, a silicone or
a silicone rubber; or other porous particulate material
such as for example inorganic oxides and inorganic
chlorides.
Preferably the support material is porous silica which has
a surface area in the range of from 10 to 700 m2/g, a
total pore volume in the range of from 0.1 to 4.0 cc/g and
an average particle size in the range of from 10 to SOOjum.
More preferably, the surface area is in the range of from
50 to 500 m2/g, the pore volume is in the range of from
0.5 to 2.5 cc/g and the average particle size is in the
range of from 20 to 200 JOTI. Most desirably the surface
area is in the range of from 100 to 400 m2/g, tine pore
volume is in the range of from 0.8 to 3.0 cc/g and the
average particle size is in the range of from 30 to 100
um. The average pore size of typical porous support
materials is in the range of from 10 to 1000 A.
Preferably, a support material is used that has an average
pore diameter of from 50 to 500 A, and most desirably from
75 to 350 A. It may be particularly desirable to dehydrate
the silica at a temperature of from 100°C to 800°C
anywhere from 3 to 24 hours.
Suitably, the support may be flexible or a rigid support,
the insoluble support is coated and/or impregnated with
the compounds of the process of the invention by
techniques well known to those skilled in the art.
Alternatively, the compounds of the process of the
invention are fixed to the surface of an insoluble
support, optionally via a covalent bond, and the
arrangement optionally includes a bifunctional spacer
molecule to space the compound from the insoluble support.
The compounds of the invention may be fixed to the surface
of the insoluble support by promoting reaction of a
functional group present in the compound of formula I or
III, for example a substituent K, D, Z and E (or: K1, D1
and E1) of the aryl moiety, with a complimentary rreactive
group present on or previously inserted into the support.
The combination of the reactive group of the support with
a complimentary substituent of the compound of the
invention provides a heterogeneous catalyst where the
compound of the invention and the support are linked via a
linkage such as an ether, ester, amide, amine, urea, keto
group.
The choice of reaction conditions to link a compound of
the process of the present invention to the support depend
upon the ethylenically unsaturated compound and the groups
of the support. For example, reagents such as
ca rbodi imi des, 1,1'-carbonyldiimidazole, and processes
such as the use of mixed anhydrides, reductive amination
may be employed.
According to a further aspect, the present invention
provides the use of the process of any aspect of the
invention wherein the catalyst is attached to a support.
Conveniently, the process of the invention may be carried
out by dissolving the Group VIB or VIIIB metal or compound
thereof as defined herein in a suitable solvent such as
one of the hydroxyl group containing compounds or aprotic
solvents previously described (a particularly preferred
solvent would be the ester or acid product of the specific
carbonylation reaction e.g. Methyl propionate for ethylene
carbonylation) and subsequently admixing with a compound
of formula I or III as defined herein and an acid.
The carbon monoxide may be used in the presence of other
gases which are inert in the reaction. Examples of such
gases include hydrogen, nitrogen, carbon dioxide and the
noble gases such as argon.
Suitable Group VIB or VIIIB metals or a compound thereof
which may be combined with a compound of formula I or III
include cobalt, nickel, palladium, rhodium, platinum,
chromium, molybdenum and tungsten, preferably include
cobalt, nickel, palladium, rhodium and platinum.
Preferably, component a) is a Group VIIIB metal or a
compound thereof. Preferably, the metal is a Group VIIIB
metal, such as palladium. Preferably, the Group VIIIB
metal is palladium or a compound thereof. Thus, component
a) is preferably palladium or a compound thereof.
Suitable compounds of such Group VIB or VIIIB metals
include salts of such metals with, or compounds comprising
weakly coordinated anions derived from, nitric acid;
sulphuric acid; lower alkanoic (up to .Cia) acids such as
acetic acid and propionic acid; sulphonic acids such as
methane sulphonic acid, chlorosulphonic acid,
fluorosulphonic acid, trifluoromethane sulphonic acid,
benzene sulphonic acid, naphthalene sulphonic acid,
toluene sulphonic acid, e.g. p-toluene sulphonic acid, tbutyl
sulphonic acid, and 2-hydroxypropane sulphonic acid;
sulphonated ion exchange resins; perhalic acid such as
perchloric acid; ; halogenated carboxylic acids such as
trichloroacetic acid and trifluoroacetic acid;
orthophosphoric acid; phosphonic acids such as
benzenephosphonic acid; and acids derived from
interactions between Lewis acids and Broensted acids.
Other sources which may provide suitable anions include
the optionally halogenated tetraphenyl borate derivatives,
e.g. perfluorotetraphenyl borate. Additionally, zero
valent palladium complexes particularly those with labile
ligands, e.g. triphenylphosphine or alkenes such as
dibenzylideneacetone or styrene or
tri(dibenzylideneacetone)dipalladium may be used.
Nevertheless, an acid is present in the catalyst system as
set out hereinbefore, even if other sources of anion such
as those noted above are also present.
Thus, the acid is selected from an acid having a pKa
measured in aqueous solution at 18°C of less than 4, more
preferably less than 3, most prefer-ably less than 2.
Suitable acids include the acids listed supra.
Preferably, the acid is not a carboxylic acid, more
preferably the acid is either a sulprionic acid, or some
other non-carboxylic acid such as those selected from the
list consisting of perchloric acid,, phosphoric acid,
methyl phosphonic acid, sulphuric acid, and sulphonic
acids, even more preferably a sulphonic acid or other noncarboxylic
acid (selected from the li_st above) having a
pKa measured in aqueous solution at 1 8°C of less than 2,
yet even more preferably a sulphonic acid having a pKa
measured in aqueous solution at 18°C off less than 2, still
more preferably the acid is selected from the list
consisting of the following sulphonic acids:
methanesulphonic acid, trifluoromethaanesulphonic acid,
tert-butanesulphonic acid, p-toluenesulphonic acid, 2-
hydroxypropane-2-sulphonic acid, and 2,4,6-
trimethylbenzenesulphonic acid, most preferably the acid
is methanesulphonic acid.
As mentioned, the catalyst system of the present
invention may be used homogeneously or heterogeneously.
Preferably, the catalyst system is used homogeneously.
The catalyst system of the present invention is
preferably constituted in the liquid phase which may be
formed by one or more of the reactants or by the use of a
suitable solvent.
The molar ratio of the amount of ethylenically
unsaturated compound used in the reaction to the amount of
hydroxyl providing compound is not critical and may vary
between wide limits, e.g. from 0.001:1 to 100:1 mol/mol.
The product of the carbonylation reaction using the
ligand of the invention may be separated from the other
components by any suitable means. However, it is an
advantage of the present process that significantly fewer
by-products are formed thereby reducing the need for
further purification after the initial separation of the
product as may be evidenced by the generally significantly
higher selectivity. A further advantage is that the other
components which contain the catalyst system which may be
recycled and/or reused in further reactions with minimal
supplementation of fresh catalyst.
Preferably, the carbonylation is carried out at a
temperature of between -10 to 150°C, more preferably 0°C
to 140°C, even more preferably 15°C to 140°C, most
preferably 20°C to 120°C. An especially preferred
temperature is one chosen between 80°C to 120°C.
Advantageously/ the carbonylation can be carried out at
moderate temperatures, it is particularly advantageous to
be able to carry out the reaction at room temperature
(20°C) .
Preferably, when operating a low temperature
carbonylation, the carbonylation is carried out between -
30°C to 49°C, more preferably, -10°C to 45°C, still more
preferably 0°C to 45°C, even more preferably 10°C to 45°C,
most preferably 15°C to 45°C. Especially preferred is a
range of 15 to 35°C.
Preferably, the carbonylation is carried out at a CO
partial pressure of between 0.80 x 105 N.m~2-90 x 105N.m"2,
more preferably 1 x 105 N.m~2-65 x 105N.m~2, most preferably
1-30 x 105 N.m"2. Especially preferred is a CO partial
pressure of 5 to 20 x 105N.nf2.
Preferably, a low pressure carbonylation is also
envisaged. Preferably, when operating a low pressure
carbonylation the carbonylation is carried out at a CO
partial pressure of between 0.1 to 5 x 105N.m~2, more
preferably 0.2 to 2 x 105N.m~2, most preferably 0.5 to 1.5
x 105N.m~2.
The ethylenically unsaturated compounds may be substituted
or non-substituted with groups as defined above for the
"aryl" group above. Particularly suitable substituents
include alkyl and aryl groups as well as groups containing
heteroatoms such as halides, sulphur, phosphorus, oxygen
and nitrogen. Examples of substituents include chloride,
bromide, iodide and hydroxy, alkoxy, carboxy, amino,
amido, nitro, cyano, thiol or thioalkoxy groups. Suitable
ethylenically unsaturated compounds include ethene,
propene, hexene, vinyl compounds such as vinyl acetates,
heptene, octene, nonene, decene, undecene, dodecene, etc
up to Cao, i.e. having from 2 to 30 carbon atoms, which
may be linear or branched, cyclic or uncyclic or part
cyclic and in which the double bond may take any suitable
position in the carbon chain and which includes all
stereisomers thereof.
Moreover, the unsaturated compound may have one or more
unsaturated bonds and therefore, for example, the range of
ethylenically unsaturated compounds extends to dienes.
The unsaturated bond(s) may be internal or terminal, the
catalyst system of the invention being particularly
advantageous in the conversion of internal olefins.
Particularly preferred are olefins having from 2 to 22
carbon atoms per molecule, such as ethene, propene, 1-
butene, 2-butene, isobutene, pentenes, hexenes, octenes,
e.g. oct-2-ene, oct-3-ene, oct-4-ene, decenes and
dodecenes, triisobutylene, tripropylene, internal Cn
olefins, and internal Cis-Cie olefins, 1,5-cyclooctadiene,
cyclododecene, methyl pentenoate and pentene nitriles,
e.g. pent-2-ene nitrile.
The ethylenically unsaturated compound is preferably an
alkene having 1 to 3 carbon-carbon double bonds per
molecule. Non-limiting examples of suitable dienes
include the following: 1,3-butadiene, 2-methyl-l,3-
butadiene, 1,5-cyclooctadiene, 1,3-cyclohexadiene, 2,4-
heptadiene, 1,3-pentadiene, 1,3-hexadiene, particularly
1,3-butadiene.
Another preferred category of unsaturated compounds
consists of unsaturated esters of carboxylic acids and
esters of unsaturated carboxylic acids. For example, the
starting material may be a vinyl ester of a carboxylic
acid such as acetic acid or propanoic acid, or it may be
an alkyl ester of an unsaturated acid, such as the methyl
or ethyl ester of acrylic acid or methacrylic acid.
A further preferred category of unsaturated compounds
consists of cycloalkadienes, which will ordinarily refuse
carbonylation. For example, the starting material may be
dicyclopentadiene or norbornadiene, to give diesters,
diamides or diacids, etc., which may find subsequent use
as monomers in polymerisation reactions.
The use of stabilising compounds with the catalyst system
may also be beneficial in improving recovery of metal
which has been lost from the catalyst system. When the
catalyst system is utilized in a liquid reaction medium
such stabilizing compounds may assist recovery of the
Group VI or VIIIB metal.
Preferably, therefore, the catalyst system includes in a
liquid reaction medium a polymeric dispersant dissolved in
a liquid carrier, said polymeric dispersant being capable
of stabilising a colloidal suspension of particles of the
Group VI or VIIIB metal or metal compound of the catalyst
system within the liquid carrier.
The liquid reaction medium may be a solvent for the
reaction or may comprise one or more of the reactants or
reaction products themselves. The reactants and reaction
products in liquid form may be miscible with or dissolved
in a solvent or liquid diluent.
The polymeric dispersant is soluble in the liquid reaction
medium, but should not significantly increase the
viscosity of the reaction medium in a way which would be
detrimental to reaction kinetics or heat transfer. The
solubility of the dispersant in the liquid medium under
the reaction conditions of temperature and pressure should
not be so great as to deter significantly the adsorption
of the dispersant molecules onto the metal particles.
The polymeric dispersant is capable of stabilising a
colloidal suspension of particles of said Group VI or
VIIIB metal or metal compound within the liquid reaction
medium such that the metal particles formed as a result of
catalyst degradation are held in suspension in the liquid
reaction medium and are discharged from the reactor along
with the liquid for reclamation and optionally for re-use
in making further quantities of catalyst. The metal
particles are normally of colloidal dimensions, e.g. in
the range 5 - 100 run average particle size although larger
particles may form in some cases. Portions of the
polymeric dispersant are adsorbed onto the surface of the
metal particles whilst the remainder of the dispersant
molecules remain at least partially solvated by the liquid
reaction medium and in this way the dispersed Group VI or
VIIIB metal particles are stabilised against settling on
the walls of the reactor or in reactor dead spaces and
against forming agglomerates of metal particles which may
grow by collision of particles and eventually coagulate.
Some agglomeration of particles may occur even in the
presence of a suitable dispersant but when the dispersant
type and concentration is optimised then such
agglomeration should be at a relatively low level and the
agglomerates may form only loosely so that they may be
broken up and the particles redispersed by agitation.
The polymeric dispersant may include homopolymers or
copolymers including polymers such as graft copolymers and
star polymers.
Preferably, the polymeric dispersant has sufficiently
acidic or basic functionality to substantially stabilise
the colloidal suspension of said Group VI or VIIIB metal
or metal compound.
By substantially stabilise is meant that the precipitation
of the Group VI or VIIIB metal from the solution phase is
substantially avoided.
Particularly preferred dispersants for this purpose
include acidic or basic polymers including carboxylic
acids, sulphonic acids, amines and amides such as
polyacrylates or heterocycle, particularly nitrogen
heterocycle, substituted polyvinyl polymers such as
polyvinyl pyrrolidone or copolymers of the aforesaid.
Examples of such polymeric dispersants may be selected
from polyvinylpyrrolidone, polyacrylamide,
polyacrylonitrile, polyethylenimine, polyglycine,
polyacrylic acid, polymethacrylic acid, poly(3-
hydroxybutyricacid), poly-L-leucine, poly-L-methionine,
poly-L-proline, . poly-L-serine, poly-L-tyrosine,
poly(vinylbenzenesulphonic acid) and poly(vinylsulphonic
acid).
Preferably, the polymeric dispersant incorporates acidic
or basic moieties either pendant or within the polymer
backbone. Preferably, the acidic moieties have a
dissociation constant (pKa) of less than 6.0, more
preferably, less than 5.0, most preferably less than 4.5.
Preferably, the basic moieties have a base dissociation
constant (pKb) being of less than 6.0, more preferably
less than 5.0 and most preferably less than 4.5, pKa and
pKb being measured in dilute aqueous solution at 25°C.
Suitable polymeric dispersants, in addition to being
soluble in the reaction medium at reaction conditions,
contain at least one acidic or basic moiety, either within
the polymer backbone or as a pendant group. We have found
that polymers incorporating acid and amide moieties such
as polyvinylpyrollidone (PVP) and polyacrylates such as
polyacrylic acid (PAA) are particularly suitable. The
molecular weight of the polymer which is suitable for use
in the invention depends upon the nature of the reaction
medium and the solubility of the polymer therein. We have
found that normally the average molecular weight is less
than 100,000. Preferably, the average molecular weight is
in the range 1,000 - 200,000, more preferably, 5,000 -
100,000, most preferably, 10,000 - 40,000 e.g. Mw is
preferably in the range 10,000 - 80,000, more preferably
20,000 - 60,000 when PVP is used and of the order of 1,000
- 10,000 in the case of PAA.
The effective concentration of the dispersant within the
reaction medium should be determined for each
reaction/catalyst system which is to be used.
The dispersed Group VI or VIIIB metal may be recovered
from the liquid stream removed from the reactor e.g. by
filtration and then either disposed of or processed for
re-use as a catalyst or other applications. In a
continuous process the liquid stream may be circulated
through an external heat-exchanger and in such cases it
may be convenient to locate filters for the palladium
particles in these circulation apparatus.
Preferably, the polymer:metal mass ratio in g/g is between
1:1 and 1000:1, more preferably, between 1:1 and 400:1,
most preferably, between 1:1 and 200:1. Preferably, the
polymer :metal mass ratio in g/g is up to 1000, more
preferably, up to 400, most preferably, up to 200.
According to a further aspect there is provided a reaction
medium comprising one or more reactants, and a catalyst
system comprising, or obtainable by combining, at least a
Group VIB or VIIIB metal or metal compound, a bidentate
phosphine, arsine, or stibine ligand, and an acid, as
defined herein, wherein said ligand is present in at least
a 2:1 molar excess compared to said metal or said metal in
said metal compound, and that said acid is present in at
least a 2:1 molar excess compared to said ligand.
Preferably, said reaction medium is a liquid-phase
reaction medium, more preferably a liquid-phase
continuous-system reaction system.
Preferably, within said reaction medium, the amount of
free acid present in the medium, that is acid which is not
directly combined with the phosphine ligand, is greater
than SOOppm, more preferably greater than lOOOppm, most
preferably greater than 2000ppm.
According to a further aspect the invention provides a
process for preparing the catalyst systems of the
invention comprising combining components a), b) and c) as
defined herein, preferably in the aforementioned ratios.
According to a yet further aspect the present invention
provides the use of a system comprising, or obtainable by
combining:
a) a metal of Group VIB or Group VIIIB or a compound
thereof,
b) a bidentate phosphine, arsine, or stibine ligand,
preferably a bidentate phosphine ligand, and
c) an acid,
wherein said ligand is present in at least a 2:1 molar
excess compared to said metal or said metal in said metal
compound, and that said acid is present in at least a 2:1
molar excess compared to said ligand, as a catalyst in the
carbonylation of an ethylenically unsaturated compound,
preferably the liquid-phase carbonylation of an
ethylenically unsaturated compound, more preferably the
liquid-phase continuous-system carbonylation of an
ethylenically unsaturated compound.
For the avoidance of any doubt, each and every feature
described hereinbefore is equally applicable to any or all
of the various aspects of the present invention as set out
herein, unless such features are incompatible with the
particular aspect or are mutually exclusive.
All documents mentioned herein are incorporated by
reference thereto.
The following examples further illustrate the present
invention. These examples are to be viewed as being
illustrative of specific materials falling within the
broader disclosure presented above and are not to be
viewed as limiting the broader disclosure in any way.
Example 1
Preparation of 1,2 bis (diadamantylphosphinomethyl) benzene
1,2 bis(diadamantylphosphinomethyl) benzene
(Method 1)
The preparation of this ligand was carried out as follows.
1.1 Preparation of (1-Ad) 2P (O) Cl
Phosphorous trichloride (83 cm3, 0.98 mol) was added
rapidly via cannula to a combination of aluminium chloride
(25.0 g, 0.19 mol) and adamantane (27.2 g, 0.20 mol)
affording a tan suspension. The reaction was heated to
reflux. After 10 mins, a yellow-orange suspension was
formed. The reaction was refluxed for a total of 6 h. The
excess PCla was removed by distillation at atmospheric
pressure (BP 75 °C). On cooling to ambient temperature, an
orange solid was formed. Chloroform (250 cm3) was added
yielding an orange suspension, which was cooled to 0 °C.
Water (150 cm3) was added slowly: initially the suspension
viscosity increased, but on full addition of water the
viscosity lessened. From this point the reaction was no
longer kept under an atmosphere of Ar. The suspension was
Buchner filtered to remove the yellow-orange solid
impurity. The filtrate consisted of a two phase system.
The lower phase was separated using a separating funnel,
dried over MgS04 and Buchner filtered. The volatiles were
removed via rotary evaporation, drying finally in-vacuo,
affording an off-white powder. Yield 35.0 g, 99 %. 31P
NMR: 5 = 85 ppm, 99 % pure. FW = 352.85.
1.2 Preparation of (l-Ad)2PH
L±A1H4 (2.54 g, 67.0 mmol) was added over 90 minutes to a
chilled (-10 °C) solution of (l-Ad)2P (0) Cl (10.00 g, 28.3
mmol) in THF. (120 cm3) . The reaction was allowed to warm
to ambient temperature then stirred for 20 h. The grey
suspension was cooled to -10 °C. HC1 (aq., 5 cm3 c. HC1 in
5O cm3 degassed water) was added slowly via syringe
(initially very slowly due to exotherm of reaction),
yielding a two phase system, with some solid material in
the lower phase. Further HC1 (~ 5 cm3 c. HC1) was added to
improve the separation of the layers. The upper phase was
removed via flat ended cannula, dried over MgSO* and
filtered via cannula. The volatiles were removed in-vacuo
affording the product as a white powder, isolated in the
glovebox. Yield 6.00 g, 70 %. 31P NMR: 6= 17 ppm, 100 %
pure. FW = 302.44.
1.3 Preparation of (l-Ad)2PCl
A solution of Ad2PH (10.5 g, 34.7 mmol) and DBU (6.12 cm3,
4O.9 mmol) in toluene (250 cm3) was chilled to -10 °C.
Phosgene solution (30.0 cm3, 56.7 mmol, was added slowly
via cannula, transferring via a measuring cylinder. This
afforded a highly viscous pale yellow suspension.
Additional toluene (100 cm3) was added via cannula to
lessen the viscosity and ease the stirring. The reaction
was filtered via cannula affording a yellow filtrate. The
residue was washed with additional toluene (2 x 100 cm3)
and the washings combined with the original filtrate. The
volatiles were removed in-vacuo affording a pale yellow
solid, which was washed with pentane (2 x 30 cm3, washings
practically colourless). The product was dried in-vacuo
and isolated in the glovebox as a lemon yellow powder.
Yield 7.84 g, 67 %. 31P NMR: 6 = 139 ppm, 99-1- % pure. FW =
336.88.
1.4 Preparation of 1,2-bis (di-1-
adamantylphosphinome thyl) benzene
1.4.1 Preparation of DI-SODIO-ORTHO-XYLENE (DISOD)
BunLi (2.5 M in hexanes, 11.28 cm3, 28.2 mmol) was added
dropwise via syringe over 15 minutes to a stirred
suspension of NaOBu* (crushed, 2.71 g, 28.2 mmol), oxylene
(1.15 cm3, 9.4 mmol) and N,N,N',N' - tetramethyl
ethylene diamine (TMEDA) (4.26 cm3, 28.2 mmol) in heptane
(100 cm3) . The reaction was heated at 60 °C for 2 h, then
allowed to cool / settle, affording a bright orange solid
(DISOD) and pale yellow solution. The solution was removed
via cannula filtration and the solid washed with
additional heptane (50 cm3) and dried in-vacuo. 90 % yield
assumed, 8.47 mmol.
1.4.2 Reaction of DI-SODIO-ORTHO-XYLENE with 2 equiv (1-
Ad)
A suspension of DISOD (8.47 mmol) in Et20 (100 cm3) was
prepared at -78 °C. A suspension of Ad2PCl (5.70 g, 16.9
mmol) in Et2O (120 cm3) was stirred rapidly at -78 °C and
added via wide-bore cannula to the DISOD suspension. The
reaction was allowed to warm to ambient temperature and
stirred for 18 h, affording a pale yellow turbid solution.
Water (degassed, 100 cm 3) added via cannula affording a
two phase system, with a great deal of white solid present
(product) due to the low solubility of this material. The
upper phase (Et2O) was removed via cannula. The solid in
the aqueous phase was extracted using dichloromethane (200
cm3), forming two clear phases. The lower phase (CH2C12)
was removed via cannula and combined with the original
Et2O phase. The volatiles were removed in-vacuo yielding a
slightly sticky solid. The solid was washed with pentane
(200 cm3) with attrition being performed, the washings
being removed via cannula filtration. The white solid was
dried in-vacuo and isolated in the glovebox as a friable
white powder. Yield 3.5 g, 59 %. FW = 707.01.
31P {1H}NMR data:- 8 24 ppm.
*H NMR data:- (400 MHz, CDC13, 298 K) 8 7.59-7.50 (m, 2H,
Ar-H), 7.09-6,99 (m, 2H, Ar-H) , 3.01 (d, 4H, 2JPH = 3.2 Hz,
CH2) , 2.07-1.57 (m, 60H, C10H15) ppm.
13C {1H} NMR data:- (100 MHz, CDC13, 298 K) 5 139.4 (dd, JPC
- 10.7 Hz, JpC = 2.3 Hz, Ar-C) , 131.0 (d, JPC = 16.8 Hz,
Ar-C), 125.0 (s, Ar-C), 41.1 (d, 2JPC = 10.7 Hz, Ad-C2) ,
37.2 (s, Ad-C4), 36.9 (d, ^pc = 22.9 Hz, Ad-C1), 28.8 (d,
3JPC = 7.6 Hz, Ad-C3), 22.0 (dd, 1JPC = 2 2 . 9 Hz, 4JPC = 3 . 1
Hz, CH2) •
Example 2
Preparation of 1,2 bis(diadamantylphosphinomethyl) benzene
(method 2)
2.1 Di-1-adamantyl phosphinic chloride was prepared in
accordance with the method of Example 1.1.
2.2 Di-1-adamantyl phosphine was prepared in accordance
with the method of Example 1.2.
2.3 (Di-1-adamantyl phosphine) trihydro boron. Borane
(THF) adduct (10 cm3, lOmmol) was added to stirred
solution of di-1-adamantyl phosphine (1.36g, 4.5mmol) in
THF (30cm3) . Stirring for a further 5hrs afforded a
slightly turbid solution. The volatiles were then removed
in-vacuo to yield the product as a pure white solid.
Yield: 1.39g, 98%, 99% pure. FW: 315.25. 31P NMR: 8 41ppm
(d, JpB 64 Hz) .
2.4 Synthesis of 1,2 bis (di-1-
adamantylphosphor (borane) methyl) benzene via deprotonation
with socBuLi and reaction with act dichloro o-xylene. To a
stirred, cooled (-78°) THF solution (60cm3) of di-1-
adamantyl phosphine trihydroboron (5g, 15.8mmol) , was
slowly added (via syringe) secBuLi (12.3cm3,16.6mmol), upon
full addition the solution had a noticeable yellow
colouration. The solution was stirred for 30 minutes at
-78° and then allowed to warm to room temperature and stir
for a further 120 minutes. The solution was then cooled to
-78° and a THF solution (20cm3) of act dichloro o-xylene
was added via cannula. The..solution was then allowed to
warm to room temperature and stirred for 15 hrs. The
volatiles where then removed in-vacuo. No further work up
was required as LiCl and excess organics are removed
during the deprotection procedure.Yield: 100% 85% pure.
31P {aH} NMR (CDC13,298K) 8 (d, br) 41 ppm.
UB ^H) NMR 8 -43 ppm (d, JBP 44 Hz)
XH NMR (CDC13/ 298K) 8 7.8-7.50 ppm (m,br Ar-H) , 8
7.49-7.00 ppm (m, br Ar-H), 8 3.3 ppm (d, CH2), 8
2.2-1.2 ppm (m, Ci0Hi5)
2.5 Synthesis of 1,2-bis(diadamantylphosphinomethyl)
benzene via deprotection of 1,2
bis (di-adamantylphosphor (borane) methyl) benzene with
HBF4'O(ME)2.
Tetrafluoroboric acid dimethyl ether complex (5
equivalents, 12.5mmols, 1.5cm3) was added slowly via
syringe to a cooled (0°c) stirred solution of 1,2 bis (diadamantylphosphor
(borane) methyl benzene (70 cm3
dichloromethane). The solution was stirred at 0°c for 1
hour and then allowed to warm to ambient temperature and
stir for a further 12 hours. The reaction mixture was then
added to a cooled (0°c) saturated solution (degassed)
NaHCOa solution (5* excess NaHCOa) and stirred vigorously
for 50 minutes. The organic phase was then extracted with
2*30 cm3 portions of diethyl ether, and added to the DCM
extract. The organic layers were then washed with 2 x 30
cm3 portions of degassed water and dried over MgS04. The
volatiles were then removed in-vacuo.
31P ^H} NMR:8 26.4 ppm (s) .
H1 NMR (CDC13, 298K) 6 7.54 ppm (q, Ar-H, JHH 3.4 Hz), 7.0
ppm (q, Ar-H, JHH 3.4 Hz) , 3.0 ppm (d, br CH2) 1.6-2.1 ppm
(m,br
Example 3
Preparation of 1,2 bis (di-3,5-
dimethyladamantylphosphinomethyl) benzene (method 2)
1,2-bis(di-1-(3,5-dimethyl-adamantyl) phosphinomethyl) benzene
3.1 Di-1- (3,5-dimethyladamantyl) phosphinic chloride was
prepared in accordance with the method of Example 2.1
except using 1,3 dimethyladamantane 21.7g (0.132 mol)
instead of adamantane, and AlCla (18.5gg, 0.14 mol) .
Yield 23.5g FW: 409.08.. 31P NMR: 8: 87ppm (s) .
3.2 Di-1-(3,5-dimethyladamantyl) phosphine was prepared
as per Example 2.2 above except using 25.0 g Di-1-(3,5-
dimethyladamantyl) phosphinic chloride instead of di-1-
adamantyl phosphonic chloride Yield 15.7 g FW: 358.58..
31P NMR: 8: 15.7ppm (s) .
3.3 Di-1- (3,5-dimethyladamantyl) phosphine } trihydro
boron was prepared as per Example 2.3 above except using
10.0 g Di-l-(3,5-dimethyladamantyl) phosphine instead of
di-1-adamantyl phosphine. Yield 9.5 g 31P NMR: 8: 40.5ppm
(br).
3.4 Synthesis of 1,2 bis (di-3,5-dime thyladamantyl
(borane)methyl) benzene via deprotonation with *acBuLi and
reaction with oca dichloro o-xylene was prepared as per
Example 2.4 above except using equimolar amounts of di-
3,5-dimethyl adamantyl phosphine trihydroboron instead of
di-1-adamantyl phosphine trihydroboron.
3.5 Synthesis of 1,2 bis (di-3,5-
dimethyladamantylphosphinomethyl) benzene via deprotection
of 1,2 bis (di-3,5-dimethyladamantyl
phosphor (borane) methyl) benzene with HBF4'O(ME)2 was
prepared as per 1,2 bis (di-1-adamantylphosphinomethyl)
benzene (Example 2.5) above except by using equimolar
amounts of 1,2 bis(di-3,5-
dimethyadamantylphosphor(borane)methyl) benzene instead of
1,2 bis(di-adamantylphosphor(borane)methyl) benzene.
Example 4
Preparation of 1, 2 bis (di-5-tertbutyladamantylphosphinomethyl)
benzene (method 2)
1,2-bis(di-1-(5-tert-butyl-adamantyl) phosphinomethyl) benzene
4.1 Di-1-(5-tert-butyladamantyl) pHosphinic chloride was
prepared as per Di-1-adamantyl phosphinic chloride above
except using tert-butyladamantane 25.37g (0.132 mol)
instead of adamantane, and AlCla (18.5gg, 0.14 mol).
Yield 22.6g FW: 464.98.. 31P NMR: 8: 87ppm (s) .
4.2.1 Di-1-(5-tert-butyladamantyl) phosphine was
prepared as per Di-1-adamantyl phosphine above except
using 13.5 g Di-1-(5-tert-butyladamantyl) phosphinic
chloride instead of di-1-adamantyl phosphinic chloride.
Yield 9.4 g FW: 414.48.. 31P NMR: 8: 18.62ppm (s) .
4.2.2 Di-1-(5-tert-butyladamantyl) phosphine) trihydro
boron was prepared as per Di-1-adamantyl phosphine above
except using 10.0 g Di-1-(5-tert-butyladamantyl) phosphine
instead of di-1-adamantyl phosphine. Yield 9.5 g 31P
NMR: 8: 41.6ppm (br).
4.2.3 Synthesis of 1,2 bis (di-5-tertbutyladamantylphosphor
(borane) me thyl) benzene via
deprotonation with MCBuLi and reaction with act dichloro oxylene
was prepared as per 1,2 bis (di-1-
adamantylphosphor (borane) methyl) benzene above except
using equimolar amounts of di-1-(5-tert-butyladamantyl)
phosphine trihydroboron instead of di-1-adamantyl
phosphine trihydroboron.
4.3 Synthesis of 1,2 bis (di-5-tertbutyladamantylphosphinomethyl)
benzene via deprotection of
1,2 bis (di-4-tert-butyladamantyl phosphor (borane) me thyl)
benzene with HBF adamantylphosphinomethyl) benzene above except 1,2 bis(di-
5-ter t-butyladamantylphosphor (borane) me thyl) benzene was
used instead of 1,2 bis(diadamantylphosphor
(borane) me thyl) benzene in equimolar
amounts.
Example 5
Preparation of 1,2 bis(1-adamantyl tert-butylphosphinomethyl)
benzene (method 2)
5.1. 1-adamantylphosphonic acid dichloaride. This compound
was synthesised according to the method of Olah et al (J.
Org. Chem. 1990, 55, 1224-1227).
5.2 1-adamantyl phosphine. LiAlH4 (3.5g, 74mmol) was
added over 2 hrs to a cooled solution (0°C) of 1-
adamantylphosphonic acid dichloride (15g, 59 mmol) in THF
(250 cm3) . The reaction was then allowed to warm to
ambient temperature and was stirred for 20 hrs. The grey
suspension was then cooled (0°C) and HC1 (75 cm3, 1M) was
slowly added via syringe, to afford a two phase system
with some solid present in the lower phase. Concentrated
HC1 (8cm3, 11M) was then added to improve the separation
of the two layers. The (upper) THF phase was removed .via
cannula and dried over magnesium sulphate. After
filtration via cannula, the volatiles were removed invacuo
to afford the product.
5.3 (1-adamantyl-tert-butyl phosphine) trihydro boron.
nBuLi (20 cm3, 32 mmol 1.6M soln) was added over 1 hour to
a cooled solution of 1-adamantyl phosphine (5.0g 30 mmol)
in THF (100 cm3) . The solution was allowed to warm to
room temperature and stirred for a further 2 hours. The
solution was recooled to 0°C and tert-butylchlpride
(2.78g, 30 mmol) was added and stirring continued for a
further 16 hours at room temperature. The material was
isolated as the borane adduct by addition of Borane (THF)
adduct (30 cm3, 30mmol) followed by removal of the
solvent. The material was isolated as a white solid which
was a mixture of isomers.
5.4 Synthesis of 1,2 bis (1-adamantyl-tert-butyl phosphor
(borane) methyl) benzene via deprotonation with 8ecBuLi and
reaction with act dichloro o-xylene. The synthesis was
carried out as per 1,2 bis (di-1-
adamantylphosphor(borane)methyl) benzene above except
equimolar amounts of 1—adamantyl-tertbutyl
(phosphine) trihydroboron were used instead of the di-
1-adamantyl phosphine trihydroboron.
5.5 Synthesis bis (1-adamantyl -ter tbutylphosphinomethyl)
benzene via deprotection of 1,2 bis
(1-adamantyl-tert-b-utyl phosphor (bor ane) methyl) benzene
with HBP4-0(ME)2. As per 1,2 bis (diadamantylphosphoriaomethyl)
benzene except using equimolar
amounts of 1,2 bis (1-adamantyl-tert -butyl
phosphor (borane) methyl) benzene instead of 1,2 bis)(diadamantylphosphor
(b orane)methyl) benzene.
Example 6
Preparation of 1,2 bis (di-1-diamantanephosphinoiaethyl)
benzene. Diamantane = congressane
1,2 bis(dicongressylphosphinomethyl) benzene
6.1 Diamantane. This was synthesised according to the
method of Tamara et al. Organic Syntheses, CV 6, 378
6.2 Di-1-(diamantane) phosphinic chloride. Prepared as
per Di-l-adamant;yl phosphinic chloride except using
diamantane 20.Og (0.106 mol) and A1C13 (16.Og, 0.12
mol). Yield 25.5g FW: 456.5.. 31P NMR: 8: 87ppm (s) .
6.3 Di-1-(diamantane) phosphine. Prepared as per Di-1-
adamantyl phosphine except using 25.0 g Di-1-(diamantane)
phosphinic chloride. Yield 14.0 g FW: 406.. 31P NMR: 6:
16.5ppm (s) .
6.4 Di-1-(diamantane) phosphine} trihydro boron. Prepared
as per Di-1-adamantyl phosphine trihydro boron except
using 15.0 g Di-1- (diamantane) phosphine. Yield 14.5 g .
31P NMR: S: 42.1ppm (br) .
6.5 Synthesis of 1,2 bis (diamantane
phosphor (borane)methyl) benzene via deprotonation with
8BCBuLi and reaction with oca dichloro o-xylene. Prepared
as per 1,2 bis (di-1-adamantylphosphor (borane)methyl)
benzene except using an equimolar amount of diamantane
phosphine trihydroboron instead of di-1-adamant yl
phosphine trihydroboron.
6.6 Synthesis of 1,2 bis (diamantanephosphinomethyl)
benzene via deprotection of 1,2 bis (diamantauie
(borane)methyl) benzene with HBF4'O(ME)2. Prepared as per
1,2 bis (di-1-adamantylphosphino methyl) benzene except
using an equimolar amount of 1,2 bis diamantd_ne
phosphor (borane) methyl) benzene instead of 1,2 bis (diadamantylphosphor(
borane)methyl) benzene.
Example 7
Preparation of 1,2-bis- (ditertbutylphosphinomethylj^
benzene
l,2-bis-(di-tert-butylphosphinomethyl)benzene
The preparation of this ligand was carried out in the
manner disclosed in WO 99/47528 in accordance with Example
18.
Example 8 (comparative)
Preparation of 1,3 bis(diadamantylphosphino) propane
Preparation of 1,3-bis- (di-1-adamantylphosphino) propane
(2)
8.1 Preparation of (l-Ad)2PLi
BunLi (2.5 M in hexanes, 42.02 cm3, 105.1 mmol) was added
dropwise via syringe to a stirred solution of AdaPH (10.59
g, 35.0 mmol) in THF (150 cm3). This resulted in a
darkening of the solution to yellow and the precipitation
of a large quantity of yellow solid, in a mildly
[cro
exothermic reaction. The reaction was stirred at ambient
temperature for 3 h. The volatiles were removed in-vacuo,
affording a very pale orange solid. The solid was washed
with pentane (2 x 50 cm3) to remove excess BunLi, resulting
in the isolation of a white powder (washings orange) which
was dried in-vacuo. The yield for this step was assumed to
be quantitative, on the basis of previous NMR experiments.
8.2 Reaction of 1,3-dlbromopropane with 2 equiv (l-Ad)2PLi
1,3-dibromopropane (degassed, 1.78 cm3, 17.5 mmol) was
added dropwise via syringe to a stirred suspension of
Ad2PLi (35.0 mmol, prepared as above) in THF (150 cm3) .
Initially a yellow solution was formed, then a great deal
of white solid crashed out (product). The volatiles were
removed in-vacuo and dichloromethane (300 cm3) added via
cannula affording a turbid solution. The turbidity was
lost on addition of water (degassed, 100 cm3) , a two phase
system being formed. The lower phase was removed via
cannula filtration. The volatiles were removed in-vacuo,
affording a white powder, which was washed with pentane
(100 cm3), dried and isolated in the glovebox. Yield 6.45
g, 57 %. 31P NMR: 5 = 24 ppm, 95+ % pure. FW = 644.94.
Example 9
Preparation of 1,2-bis-(dimethylaminomethyl)ferrocene
n-Butyllithium (Aldrich, 2.5 molar in hexane, 24 ml, 54
mmol) is added to a solution of
(dimethylaminomethyl)ferrocene (Aldrich, 13.13 g, 10.69
ml, 48.97 mmol) in diethyl ether (80 ml) under nitrogen at
a temperature of 25°C and the reaction mixture stirred for
4 hours. The resulting red solution is then cooled to
approximately -70°C in a dry ice/acetone bath and
[0Eschenmosers salt (ICH2NMe2) (Aldrich, 10 g, 54 mmol) is
added. The reaction is allowed to warm to room
temperature and stirred overnight.
The resultant solution is quenched with excess aqueous
sodium hydroxide and the resulting product extracted with
diethyl ether (3 x 80 ml) dried over anhydrous magnesium
sulfate, filtered over celite, and volatiles removed in
vacua to yield the crude title compound as a light orange
crystalline solid. The crude product is recrystallised
from light petrol with cooling to -17 °C and the
recrystallised product washed with cold petrol to yield
the title compound as a light orange solid (13.2 g, 74%) .
The compound can be further purified by sublimation to
give 8.5 g (52%) of the title compound (mpt 74°C).
XH NMR(250 MHz; CDC13) :64.23(brd, 2H) ; 4.11-4.10 (t, 1H) ;
4.04(s, 5H); 3.43, 3.38, 3.23, 3.18 (AB quartet, 2H);
2.22(s, 6H) .
13C NMR (63 MHz; CDC13) :583.81; 70.40; 69.25; 66.84; 57.35;
45.23.
Elemental analysis: Found: C 63.7%; H 8.9%; N 9.5%
Calculated: C 64.0%; H 8.1%; N 9 . 4%
Example 10
Preparation of 1,2-bis-(ditertbutylphosphinomethyl)ferrocene
Di-tertbutylphosphine (Aldrich, 0.616 ml, 3.33 mmol) was
added to a solution of 1,2-
bis (dimethylaminomethyl) ferrocene (Example 9, 0.5 g, 1.66
mmol) in anhydrous acetic acid (100 ml) under nitrogen and
the resulting mixture is stirred at 80°C for 72 hours. The
anhydrous acetic acid is removed in vacua at approximately
70°C to yield the crude title product as an orange/yellow
solid. The crude product is recrystallised from, ethanol
with cooling to -17°C, filtered and the filtrate washed
with cold ethanol to yield the title compound as a pale
yellow solid (0.365 g, 44%, 84°C).
XH NMR (250 MHz; CDC13) : 64.4 (2H, d, J - 2Hz) ; 3.95(5H,
s); 3.75 (1H, t, 2Hz); 2.8 (2H, dd, 12Hz, 2Hz); 2.6 (2H,
dd, 12Hz, 2Hz); 1.1 (36H, m).
13C NMR (63 MHz; CDC13) : 586.73 (d, 5.46 Hz); 70.08 (d,
4.41 Hz); 69.4665(3); 63.75(s); 31.80 (d, 2Hz); 31.45 (d,
1.98Hz); 29.89 (d, 1.88 Hz).
31P NMR (101 MHz; CDC13) : 615.00 ppm.
Elemental analysis: Found: C:66.79%; H:9.57%
Calculated: C:66.93%; H:9.63%
Example 11
Preparation of l-hydroxymethyl-2-dimethylaiidLnomethyl
ferrocene
n-Butyl lithium (Aldrich, 1.6 molar in diethyl ettier, 5.14
ml, 8.24 mmol) is added to a solution of 1-
dimethylaminomethyl ferrocene (Aldrich, l.Og, 4.12mmol) in
diethyl ether (20mL) under argon. The reaction is stirred
for 3 hours and develops a reddish colour. The solution
is then cooled in a dry ice/acetone bath, calcined paraformaldehyde
(0.247g, 2 times excess) added and the
resultant mixture stirred overnight at room temperature.
The reaction is then quenched with water, extracted with
diethyl ether, dried over MgSO4, and filtered over celite.
The solvent is removed in vacua to yield crude title
compound. The crude product is applied to a neutral
alumina column, which is eluted with petrol/diethyl ether
(9:1 ratio) to remove the starting material, 1-
dimethylaminomethyl ferrocene. The column is then eluted
with substantially pure ethyl acetate to elute the title
compound. The ethyl acetate is removed in vacuo, to yield
the title compound as an orange oil/crystalline mass.
1H NMR (250 MHz; CDC13) 82.131 (s, 6 H) , 82.735 (d, 1 H,
12.512 Hz), 83.853 (d, 1 H, 12.512 Hz), 83.984 (dd, 1 H,
2.156 Hz), 84.035 (s, 5 H), 84.060 .(dd, 1 H, 2.136 Hz)
84.071 (d, 1 H, 12.207 Hz), 84.154 (m, 1 H) , 84.73 (d, 1
H, 12.207 Hz).
13C NMR (61 MHz; CDC13) 87.688, 884.519, 870.615, 868.871,
868.447, 865.369, 860.077, 858.318, 844.414
COSY 2D XH NMR
Partly obscured doublet at 4.071ppm and its coupling to
the doublet at 4.73 ppm confirmed.
Infrared spectra (CHC13) (c.a. 0.06g / O.SmL)
2953.8 cm"1, 2860.6 cm"1, 2826.0 cm"1, 2783.4 cm"1, 1104.9
cm"1
Example 12
Preparation of 1,2-bis-(ditertbutylphosphinomethyl)ferrocene
Di-tertbutylphosphine (Aldrich, 0.54 ml, 2.93 mmol) is
added to a solution of l-hydroxymethyl-2-
dimethylaminomethyl ferrocene (Example 11, 0.2 g, 0.753
mmol) in anhydrous acetic acid (15 ml) and acetic
anhydride (0.753 mmol) under argon and the resulting
mixture is stirred at 80°C for 72 hours. The anhydrous
acetic acid is removed in vacuo at approximately 70°C to
yield the crude title product as an orange/yellow solid.
The crude product is recrystallised from ethanol with
cooling to -17°C, filtered and the filtrate washed with
cold ethanol to yield the title compound as an orange
solid (0.23 g)
aH NMR (250 MHz; CDC13) 64.351 (d, 2 H, 2Hz) , 64.022 (s, 5
H),83.827 (t, 1 H, 2 Hz), 62.858 (ddd, 2 H, ^15.869 Hz,
JHPi3.320 Hz, JHP2 1-831 Hz), 62.679 (dd, 2 H, JHH 15.869 Hz,
t
JHP 2.441 Hz), 81.166 (d, 18 H, 12.817 Hz), 61.123 (d, 18
H, 12.512 Hz)
FTIR (Chloroform, NaCl plates)
1104.1 cm"1, 2863cm"1, 2896.0 cm"1, 2940.0 cm"1, 2951.8 cm"1
31P NMR (101 MHz; CDC13) : 615.00 ppm.
Elemental analysis: Found: C:66.5%; H:9.6%
Calculated: C:66.9%; H:9.6%
Example 13
Preparation of l-hydroxymethyl-2,3-bis-
(dimethylaminomethyl) ferrocene
To a stirred solution of 1,2-bis-(dimethylaminomethyl)
ferrocene (Example 9, 0.70g, 2.32 mmol) in diethyl ether
(15 cm3) under argon is added 1.2 equivalents n-butyl
lithium (Aldrich, 1.75mL, 1.6M in diethyl ether) and the
mixture stirred for three hours to yield a red solution.
The reaction mixture is cooled in a dry ice/acetone bath,
calcined paraformaldehyde added in 2:1 excess, and the
resultant mixture stirred at room temperature overnight.
The mixture is quenched with water and extracted with
diethyl ether. The ethereal extracts are dried over MgSO«,
filtered over celite and the solvent removed in vacua, to
yield the title compound (0.7g, 2.12 mmol, 91%) as an
orange oil., which partially crystallized on cooling.
XH NMR (250 MHz; CDC13) 8 2.133 (s, 6 H) , 8 2.171 (s, 6 H) 8 2.910 (d, 1 H, 12.817 Hz), 8 2.998 (d, 1 H, 12.512 Hz),
8 3.425 (d, 1 H, 12.817 Hz), 8 3.812 (d, 1 H, 12.512 Hz),
8 3.962 (s, 5 H), 8 3.99 (d, 1 H, 12.207 Hz) (partly
obscured by large cp-ring peak at 8 3.962), 8 4.068 (d, 1
H, 82.136 Hz), 8 4.125 )d, 1 H, 8 2.136 Hz), 8 4.747 (d, 1
H, 12.207 Hz)
13C NMR (60 MHz; CDC13) 844.529, 845.244, 855.798, 857.906,
860.271, 867.944, 868.277, 869.612, 884.850, 888.322
Infrared spectra (CDC13 / thin film NaCl plates )
3380.6 cm"1 (br), 2955.7 cm"1 (m) , 2862.6 cm"1 , 2825.9 cm"1
(m), 2774.3 cm"1 (m), 1353.5 cm"1 (m) , 1104.9 cm"1 (m) ,
1038.9 cm"1 (m), 1006.8 cm"1 (s)
Elemental analysis: Found: C: 62.3%; H: 7.8%; N: 8.8%
Calculated: C:61.8%; H:7.9%; N:8.5%
Example 14
Preparation of
1,2, 3-tris-(ditertbutylphosphinomethyl) ferrocene
Di-tert-butylphosphine (Aldrich, 2.60 mL, 13.98 mmol) and
acetic anhydride (0.24 mL, 2.33 mmol) is added to a
solution of l-hydroxymethyl-2,3-bis-
(dimethylaminomethyl) ferrocene (Example 13, 0.70g, 2.12
mmol) in acetic acid (freshly distilled from acetic
anhydride 25 cm3 ), under argon. The solution is then
stirred at 80°C for 7 days, during which time the solution
becomes a dark orange colour. The solvent is then removed
in vacuo and recrystallisation effected from refluxing
ethanol together with cooling to -17°C overnight to yield
the title compound (0.43 g, 0.7 mmol, 31%) as a
yellow/orange powder.
aH NMR (250 MHz, CDC13) 8 1.12 (dd - pseudo triplet, 36 H,
12.1 Hz), 81.26 (d, 18H, 10.7 Hz), 82.68 (d, 2 H, 17.7
Hz), 82.95 (s, 2 H), 83.07, (m, 2 H) , 84.01 (s, 5 H) 8
4.33 (s, 2 H)
Infrared spectra (CHC13 / thin film NaCl plates )
1365.5 cm"1, 1470.3 cm"1, 2357.1 cm"1 ,2862.8 cm"1 , 2896.7
cm"1 , 2939.1 cm"1
Example 15
Preparation of 1,2-bis-(dicyclohexylphosphinomethyl)
ferrocene
The title compound was prepared in accordance with the
procedure of Example 10 employing dicyclohexylphosphine
(Strem of 48 High Street Orwell, Royston, United Kingdom
SG8 5QW, 659 mg, 3.33 mmol), 1,2-
bis (dimethylaminomethyl) ferrocene (0.5 g, 1.66 mmol) and
anhydrous acetic acid (100 ml). Yield 0.421 g.
Example 16
Preparation of 1,2-bis-(di-iso-butylphosphinomethyl)
ferrocene
The title compound was prepared in accordance with the
procedure of Example 10 employing di-iso-butylphosphine
(Strem 486 mg, 3.33 mmol), 1,2-
bis (dimethylaminomethyl) ferrocene (0.5 g, 1.66 mmol) and
anhydrous acetic acid (100 ml). Yield 0.372 g.
Example 17
Preparation of 1,2-bis-(dicyclopentylphosphinomethyl)
ferrocene
The title compound was prepared in accordance with the
procedure of Example 10 employing dicyclopentylphosphine
(Strem 566 mg, 3.33 mmol), 1,2-
bis (dimethylaminomethyl) ferrocene (0.5 g, 1.66 mmol) and
anhydrous acetic acid (100 ml). Yield 0.432 g.
Example 18
Preparation of 1,2-bis-(diethylphosphinomethyl) ferrocene
The title compound was prepared in accordance with the
procedure of Example 10 employing diethylphosphine (Strem
299 mg, 3.33 mmol), 1,2-bis(dimethylaminomethyl)ferrocene
(0.5 g, 1.66 mmol) and anhydrous acetic acid (100 ml).
Yield 0.254 g.
Example 19
Preparation of 1,2-bis (di-isopropylphosphinomethyl)
ferrocene
The title compound was prepared in accordance with the
procedure of Example 10 employing di-iso-propylphosphine
(Digital Speciality Chemicals 392 mg, 3.33 mmol), 1,2--
bis (dimethylaminomethyl) ferrocene (0.5 g, 1.66 mmol) and
anhydrous acetic acid (100 ml). Yield 0.262 g.
Example 20
Preparation of 1,2-bis-(dimethylphosphinomethyl)ferrocene
The title compound was prepared in accordance with the
procedure of Example 10 employing dimethylphosphine
(Digital Speciality Chemicals, 206 mg, 3.33 mmol), 1,2--
bis (dimethylaminomethyl) ferrocene (0.5 g, 1.66 mmol) and
anhydrous acetic acid (100 ml). Yield 0.285 g.
Example 21
Preparation of 1,2-bis-(diadamantylphosphinomethyl)ferrocenebis-
methanesulphonate
Di-adamantylphosphine (prepared according to J.R.Goerlich,
R.Schmutzler; Phosphorus Sulphur and Silicon; 1995, 102,
211-215, 20.Og, 0.066 mol) was added to a solution of 1,2-
bis (dimethylaminomethyl) ferrocene (Example 9, 10 g, 0.033
mol) in anhydrous acetic acid (100 ml) under nitrogen and
the resulting mixture is stirred at 80°C for 72 hours. The
orange yellow precipitate which forms is filtered and
dried in vacua at approximately 70°C to yield the title
compound as an orange/yellow solid. The title compound is
insoluble in a range of organic solvents and it is
therefore purified by conversion to the bismethanesulphonate
salt by addition of excess
methanesulphonic acid to a methanol slurry of the crude
product. This resulted in complete dissolution of the
product salt which was then isolated by removal of the
methanol in vacua followed by washing with ether and
drying to give the title compound as a pale yellow solid
(14.Og, 54%).
XH NMR (250 MHz; CD3CN): 64.57 (2H, d, J = 2Hz); 4.35 (5H,
s); 4.27 (1H, t, 2Hz); 3.34 (4H, br); 2.6 (6H, br,); 2.35-
2.18 (18H br); 2.16-2.0 (18H, br); 1.92-1.72 (24H, br). •
31P NMR (101 MHz; CD3CN) : 626.58 ppm.
Elemental analysis: Found: C:64.15%; H:7.88% Calculated:
C:64.29%; H:7.94%
Example 22
Preparation of 1,2 bis(di-1-adamantylphosphinomethyl)
ferrocene-bis-methane sulphonate
The preparation of this ligand was carried out as follows:
22.1 Preparation of (1-Ad)2P(O)C1
The di-1-adamantyl phosphine chloride was prepared in
accordance with the method of Example 1.1.
22.2 Preparation of (l-Ad)2PH
The di-1-adamantyl phosphine was prepared in accordance
with the method of Example 1.2.
22.3 Preparation of 1,2-bis (di-1-
adamantylphosphinomethyl) ferrocene-bis-methanesulphonate
The title compound was prepared in accordance with the
procedure exemplified in Example 21.
Example 23
Preparation of 1,2-bis (di-1- (3,5-dimethyladamantyl)
phosphinomethyl) ferrocene-bis-methanesulphonate
23.1 Di-1- (3,5-dimethyladamantyl) phosphinic chloride
was prepared in accordance with the method of Example 3.1.
23.2 Di-1- (3,5-dimethyladamantyl) phosphine
was prepared in accordance with the method of Example 3.2.
23.3 1,2-bis-(di-1-(3,5-dimethyla
daman tylphosphinome thy 1) f errocene-bis-methanesulphonate
The title compound was prepared in accordance with the
procedure exemplified in Example 21 except using di-1-
2 (3, 5-dimethyl-adamantyl)phosphine (23.69 g, 0.066 mol)
instead of di-adamantylphosphine. Yield 15 g.
Example 24
Preparation of 1,2-bis (di-1- (5-tert-butyl-adamantyl)
phosphinomethyl) f errocene-bis-methanesulphonate
24.3. Di-1-5-tert-butyladamantyl) phosphinic chloride
was prepared as per Example 4.1 above.
24.2 Di-1-(5-tert-butyladamantyl) phosphine
was prepared as per Example 4.2 above.
24.3 1,2-bis (di-1- (4-tert-butyl-adamantyl)
phosphinomethyl) f errocene-bis-methanesulphonate
The title compound was prepared in accordance with the
procedure exemplified in Example 21 except using di-1-(4-
tert-butyladamantyl)phosphine (27.39 g, 0.066 mol) instead
of di-adamantyl phosphine. Yield 14.52 g.
Example 25
Preparation of 1,2-bis- (1-adamantyl tert-butylphosphinomethyl)
f errocene-bis-methanesulphonate
25.1 1-adatnantylphosphonic acid dichloride
This compound was synthesised according to the method of
Olah et al (J. Org. Chem. 1990, 55, 1224-1227).
25.2 1-adamantyl phosphine
LiAlH4 (3.5 g, 74 mmol) was added over 2 hours to a cooled
solution (0°C) of 1-adamantylphosphonic acid dichloride
(15 g, 59 mmol) in THF (250 cm3) . The reaction was then
allowed to warm to ambient temperature and was stirred for
20 hours. The grey suspension was then cooled (0°C) and
HC1 (75 cm3, 1M) was slowly added via syringe, to afford a
two phase system with some solid present in the lower
phase. Concentrated HC1 (8 cm3, 11M) was then added to
improve the separation of the two layers. The (upper) THF
phase was removed via cannula and dried over magnesium
sulphate. After filtration via cannula, the volatiles were
removed in-vacuo to afford the product.
25.3 1-adamantyl tert-butyl phosphine
nBuLi (20 cm3, 32 mmol 1.6M soln) was added over 1 hour to
a cooled solution of 1-adamantyl phosphine (5.0 g, 30
mmol) in THF (100 cm3) . The solution was allowed to warm
to room temperature and stirred for a further 2 hours. The
solution was recooled to 0°C and tert-butylchloride (2.78
g, 30 mmol) was added and stirring continued for a further
16 hours at room temperature. The reaction mixture was
quenched with water and the aqueous phase extracted with
dichloromethane (2 x 50 ml) . The organic phase was dried
over sodium sulphate and evaporated iu-vacuo to yield the
title compound.
25.4 1,2-bis- (- 1-adamantyl tert-butyl-phosphinomethyl)
ferrocene-bis-methanesulphonate
The title compound was prepared in accordance with the
procedure exemplified in Example 21 except using 1-
U3
adamantyl tert-butyl phosphine (14.78 g, 0.066 mol)
instead of d±-adamantyl phosphine. Yield 9.80 g.
Example 26
Preparation of 1,2-bis-(di-1-diamantylphosphinomethyl)
ferrocene-bis-methanesulphonate
26.1 Di.am.an'bane
This was synthesised according to the method of Tamara et
al. Organic Syntheses, CV 6, 378.
26.2 Di-1—(diamantane) phosphinic chloride
Prepared as per Di-1-adamantyl phosphinic chloride of
Example 1.1 except using diamantane 20.0 g (0.106 mol) and
A1C13 (16.0 g, 0.12 mol). Yield 25.5 g FW: 456.5.. 31P NMR:
8: 87 ppm (s )
26.3 Di-1-(diamantane) phosphine
Prepared as per Di-1-adamantyl phosphine of Example 1.2
except using 25.0 g Di-1-(diamantane) phosphinic chloride.
Yield 14.0 g FW: 406.. 31P NMR: 8: 16.5 ppm (s) .
26.4 1,2-bis- (di-1-diamantylphosphinomethyl) ferrocenebis
-methanesxilphonate
The title compound was prepared in accordance with the
procedure exemplified in Example 21 except using di-1-
diamantane phosphine (26.79 g, 0.066 mol) instead of diadamantyl
phosphine. Yield 12.5 g.
t lM
Example 27
Preparation of 1,2-bis-(di-(1, 3, 5,7-tetramethyl-6,9,10-
trioxa-2-phospha-adamantylmethyl) ) ferrocene
l f 3,5,7-tetramethyl-2,4,8-trioxa-6-phospha-adamantane
(obtained from Cytec, 14.Og, 0.066 mol) was added to a
solution of 1, 2-bis (dimethylaminomethyl) ferrocene (Example
9, 10 g, 0.033 mol) in anhydrous acetic acid (100 ml)
under nitrogen and the resulting mixture is stirred at
80°C for 72 hours. The anhydrous acetic acid is removed in
vacua at approximately 70°C to yield the crude title
product as an orange/yellow solid. This is washed with
hot methanol to give the product as a mixture of isomers
as an orange solid. (12.0 g, 58%).
-XH NMR (250 MHz; CDC13) : 64.25-3.95 (8H, br, m); 3.46 (4H,
br); 1.57-2.0 (8H, br, m); 1.43-1.23 (24H, br m) .
31P NMR (101 MHz; CDC13) : 5 -27.41 (br) , -29.01 (s) , -33.9
(br) ppm.
Elemental analysis: Found: C:57.80%; H:7.35% Calculated:
C:57.87%; H:7.40%
Example 28
Preparation of I,2-bis-(dimethylaminomethyl)ferrocene-bis
methyl iodide
Methyl iodide (23.28g, 0.164 mol) is added to a solution
of 1,2-bis-(dimethylaminomethyl) ferrocence (Example 9,
20g, 0.082 mol) in degassed methanol (100 ml), and the
mixture stirred at room temperature under a nitrogen
atmosphere for 24 hours. The resulting precipitate is
removed by filtration, washed with ether and dried to
yield the title compound (43.Og).
Elemental analysis: Found: C:36.8%; H:5.1%; N,4.8%
Calculated: C:37.0%; H:5.2%; N,4.8%
13C NMR (D2O): 653.27, 853.21, 853.15, 864.68, 871.77,
873.24, 874.13, 874.95
Example 29
Preparation of 1,2-bis(dihydroxymethylphosphinomethyl)
ferrocene
Potassium hydroxide (8.52g, 0.152 mol) is added to a
solution of tetrakis(hydroxymethyl) phosphonium chloride
(Aldrich, 38.54g of 80% w/w aqueous solution, 0.162 mol)
in degassed methanol (40 ml) , and stirred at room
temperature under a nitrogen atmosphere for 1 hour. The
resultant mixture is added dropwise to a degassed solution
of 1,2-bis-(dimethylaminomethyl)ferrocene-bis-methyl
iodide (Example 28, 19.98g, 52.2 mmol) in methanol (40 ml)
under nitrogen at room temperature with stirring. The
resultant mixture is refluxed under nitrogen for 20 hours,
and the solvent removed in vacuo to form a red
precipitate. Water (30 ml), diethyl ether (85 ml) and
triethylamine (35 ml) is added to the precipitate and the
solution stirred at room temperature for 1 hour. The
aqueous layer is removed and re-extracted with diethyl
ether (2 x 30 ml) . The combined ethereal extracts are
washed with water (3 x 20 ml) dried over sodium sulphate
and filtered. The ether is removed in vacuo to yield the
crude title compound (14.33g, 94% yield) as a
microcrystalline orange solid. The crude product is
recrystallised from a warm dicholormethane/methanol
solution with the addition of light petroleum and cooling
to yield the title compound (10.69g, 70% yield) as yelloorange
crystals.
Elemental analysis: Found: C:48.44%; H:4.12%; N,0.0%
Calculated: C:48.24%; H:4.02%;
N , 0 . 0%
1H NMR: 51.75 (a, br) , 62.70 (dd, 2 H, J2HH 14.2 Hz, J2
HP
6.6 Hz), 62.85 (dd, 2 H, J2
HH 14.2 Hz, J2
HP 7.9 Hz), 63.71
(t, 1 H, JHH 2 . 4 4 Hz), 63.58 (s, 5 H) , 63.98 (d, 2 H, JHH
2.40 H z ) , 4 . 0 6 (m, 8 H) .
aH{31P} NMR: 61.75 (s, br) , 62.70 (d, 14.3 Hz), 62.85 (d,
14.3 Hz), 64.04 (m, 1 H) , 64.06 (s, 8 H) , 54.08 (s, 5H),
64.1 (m, 2 H)
13C NMR: 523.7 (d, J1
K 15.6 Hz), 663.0 (d, J^c 15.6 Hz),
666.0 (s), 667.2 (d, J3
PC 9.2 Hz), 669.6 (s) , 582.6 (d, J2pc
14.7 Hz)
31P NMR: 6-14.7
Infrared spectra (CHCls / thin film NaCl plates )
3337.8 cm'^st, br), further peaks 1104 cm'1 2929.0 cm"1,
3603.7 cm"1 ,3683.7 cm"1.
Example 30
Preparation of 1,2-bis (diphosphinomethyl)ferrocene
1,2-bis (dihydroxymethylphosphinomethyl) ferrocene (Example
29, 5.45g, 13.70 mmol) and sodium metabisulfite (5.21g,
mmol) is added to a two-phase solvent system
consisting of distilled water (60 ml) and light petroleum
(60 ml) . The mixture is refluxed for 3 hours in air. The
resultant mixture is cooled stirred and the aqueous layer
removed. The organic layer is washed with distilled water
and the organic solvent removed in vacuo to yield the
title compound (2.66g, 70% yield) as an orange crystalline
solid.
Elemental analysis: Found: C:51.65%; H:5.75%
Calculated: C:51.80%, H:5.76%
*H NMR (250 MHz; CDC13) : 5 2.7-2.8 (m, 4H) , 5 3.17 (m,
2H), 6 3.18 (m, 2H) , 5 4.04 (t, 1H, J=2.54 Hz), 5 4.09 (d,
5H, JHP 0.4 Hz), 6 4.13 (d, 2H, J=2.54 Hz)
31P NMR (101 MHz; CDC13) : 6 130.0 (t, JHP 193.0 Hz)
13C NMR (60 MHz; CDC13) : 6 12.9, 5 65.6, 5 67.3, 6 69.4, 6
86.9
13C DEPT NMR (CDC13) : 6 12.9 (CH2) , 6 65.6 (CH) , 6 67.3
(CH), 5 69.40 (5 x CH)
FTIR (Chloroform, NaCl plates): 2298.5 cm"1 (strong)
Mass spectrum: Found m/z: 278.0088; Calculated m/z
278.0077
Example 31
Preparation of l/2-bis-a/g-(P- ,6, 6,-
tetramethylphosphinan-4-one)) dimethylf errocene
1,2-bis-, -(P-(2,2,6,6,-tetramethylphosphin£in-4-onc))diinethylferrocenc
2,6-Dimethyl-2,5-heptadiene-4-one (14.69, 0.106 mol) is
added to 1,2-bis-(diphosphinomethyl) ferrocene (Example 30,
14.7g, 0.053 mol) and the mixture heated to 120°C under
nitrogen for 20 hours. The reaction mixture is cooled, the
crude title compound removed by filtration, washed with
pentene (20 ml) and dried in vacuo to yield the title
compound as a yellow-orange solid (24.9g, 85% yield). The
title compound was characterised by 31P NMR and mass
spectrum.
XH NMR (250 MHz; CDC13) : d 4.32 (1H, br) ; 4.08 (5H, br)
4.02 (1H, br); 3.94 (IHbr); 2.84 (4H, br); 1.8-2.5 (8H,
br); 1.05-1.4 (24H, br, ).
31P NMR (101 MHz; CDC13) : s 4.15 ppm.
Elemental analysis: Found: C:64.26%; H:7.88%
Calculated: C:65.03%; H:7.94%
Example 32
Preparation of 1,2-bis- (di-1, 3,5,7-tetramethyl-6, 9,10-
trioxa-2-phospha-adamantylmethyl) ) benzene
The preparation of this ligand was carried out in the
manner disclosed in WO-A-03/070370 in accordance with
Example 4 therein.
Example 33
Preparation of methyl propanoate from ethylene, carbon
monoxide and methanol catalysed by a compound of the
present invention
Condition 1 ratio of ligand:palladium = 5.2:1, ratio of
acid:palladium = 160:1 and ratio acid:ligand =30:1
Condition 2 ratio of ligand:palladium = 5.2:1, ratio of
acid:palladium = 480:1 and ratio acid:ligand = 90:1
A mechanically stirred autoclave (Hastelloy) of 2 litre
capacity was evacuated of air and then charged with a
solution of tri (dlbenzylideneacetone) dipalladium (1.44 x
10~5 moles), 1,2-bis- (di-tertbutylphosphinomethyl)
ferrocene of Example 10, (7.61 x 10"5 moles) and methane
sulfonic acid (2.30 x 10"3 moles condition 1, 6.90 x 10"3
moles condition 2) in 300 ml of methyl propanoate/methanol
(70 wt% methyl propanoate) . The autoclave was heated to
100°C and when at that temperature, ethylene (8 x 105Nm"2)
was added on top of the vapour pressure of the solvents
and immediately an equimolar mixture of carbon monoxide
and ethylene (2 x 105Nm"2) added to the system through a
pressure regulating valve set to 10 x 105Nm~2 above the
solvent vapour pressure. Suitably, the molar ratio of
ethylene to carbon monoxide in the reactor is
approximately 9:1. The temperature of the reactor was
maintained at 100°C and as the reaction proceeded
additional carbon monoxide and ethylene was added (on an
equimolar basis) through the pressure regulating Tescom
valve. No catalyst precipitation was observed.
Initial reaction rates measured in moles of methyl
propanoate (MeP) per mole of palladium, per hour and
turnover measured in moles of methyl propanoate per mole
of palladium were determined for the catalyst. This may be
accomplished by an analysis of the amount of gas consumed
per unit time (rate) and the total amount of gas consumed
during the reaction, assuming ideal gas behaviour and 100%
selectivity to methyl propanoate.
Table 1 shows the effect in increasing the relative acid
concentration compared to phosphine ligand concentration
(and metal concentration) for a batch process on both the
maximum initial rate and the turnover number (TON) after
hour, wherein initial reaction rates are measured in moles
of methyl propanoate (MeP) per mole of palladium per hour
and TON is measured as moles of methyl propanoate per mole
of palladium. For both TON and maximum initial rate,
values are significantly increased passing from condition
1 to condition 2, i.e. when increasing both the
acid:palladium and acid:ligand ratios at constant
ligand:palladium values.
(Table Removed)
Example 34
Pd(OAc)2(22mg,O.lmmol) and the respective phosphine ligand
(O.Smmol) were weighed out in tlie inert atmosphere glove
box into SOOmL 3-neck round bo>ttom flasks. On removal,
300mL of degassed MeOH were addesd and the mixture stirred
for 1 hour. To the solution metrianesulphonic acid (640|il,
lOmmol) was added. The weight of the catalyst solution was
taken. The autoclave was charged with the solution and
heated to 100C with stirring (3 .0 barg vapour pressure).
The reaction was started by the introduction of
CO/ethylene (1:1) gaseous mixture to the autoclave. The
total pressure of the autoclave vras controlled by a TESCOM
(9.8 barg) . This resulted in a 9:1 ratio of ethylene to
CO. The temperature and pressure were maintained 3 hours
during which period these values were recorded.
The gases were isolated and "the unit cooled to room
temperature. The depressurised unit was emptied and the
final weight of the solution taken.
Ligand 1 = 1, 2-bis (di-tert-butylphosphinomethyl) benzene
Ligand 2 = 1,2-bis (di-tert-butylphosphinomethyl) ferrocene
Ligand 3 = 1,2-bis (diadamantylphosphinomethyl) ferrocene
Ligand 4 = 1,2-bis(diphosphaadamantylphosphinomethyl)
ferrocene
Ligand 5 = 1,3-bis (di-tert-b>utylphosphino) 2-methylenepropane
(comparative), prepared as in WO-A-03/040159
(Example 1 therein).
The results are shown in the tables below.
(Table Removed)
a) run at 3 x palladium concentration {67.3 tng Pd(OAc)2}
For the ligand 1,3-bis (di-tert-butylphosphino)2-methylenepropane
(ligand 5) additional ligand with or without
excess acid results in a drop in catalyst performance.
The optimum conditions of low ligand and acid, e.g. Run
Nos. 3 and 4, result in the highest catalyst productivity
under the conditions studied. Addition of excess ligand
at high acid ratio as in Run No. 1 results in a
significant drop in performance, as does addition of
excess ligand at low acid ratios.
The following two tables contain data for the ligand 1,2-
Bis(di-tert-butylphosphinomethyl) benzene. The data was
collected at 80C hence th* rates and turnover numbers are
lower than the data we have already included. However,
the data shows that at constant acid:ligandb levels, an
increase in ligand:Pd ratio provides large increases in
initial rate and TON values. This data also used the
preformed catalyst [(L-L)Pd(dba) (for details see below)
and adds the ligand excess as the protonated salt. The
experimental detail is provided below.
(Table Removed)
The number of moles of palladium is equal to the number of
moles of L2Pd(dba).
The work described in these examples was carried out in 2L
capacity autoclaves. In each test lOmg of L2Pd(dba)
catalyst and 32mg (4 equivalents) or 72mg (9 equivalents)
of protonated phosphine were added to the preparation
flask in a nitrogen purged glove box. 175mL of azeotrope
product consisting of 50:50 wt% methanol and methyl
propanoate and 125mL of methyl propanoate were then
degassed and added to the flask to provide a reaction
solution which was close to 70wt% methyl propanoate.
After addition of the required quantity of
methanesulphonic acid the solution was transferred to the
evacuated autoclave and heated to 80°C in vacuo. During
this period and at all subsequent times the autoclave was
stirred at -1000 r.p.m. When this temperature had been
reached the total pressure of the system was increased to
9 bar (from the vapour pressure baseline of ~1 bar) by the
addition of ethylene and then topped up with 2bar of 1:1
C2H4/CO such that the total pressure was ~llbar and the
headspace C2H4/CO ratio was 9:1. After this time only the
1:1 gas was fed to the system at the rate which was
required to hold the pressure within the system constant.
Reaction rates and catalyst TONs were calculated from the
rate of removal of gas from the feed reservoir assuming
ideal gas behaviour and 100% selectivity for methyl
propanoate formation.
Preparation of 1,2-bis(di-1-
adamantylphosphinomethyl) benzene palladium (dba)
THF (100 cm3) was added to a combination of ligand (2.05
g, 2.90 mmol) and palladium dba (1.61 g, 2.90 mmol [Pd])
affording a deep red-orange turbid solution. The reaction
was stirred for 3 h. The reaction was filtered via
cannula, yielding a deep red-orange filtrate and a small
quantity of [Pd] residue. The volatiles were removed invacuo
affording a deep red powdery solid. Pentane (50 cm3)
was added via cannula and attrition performed with a
spatula, resulting in an orange powder separating out. The
amber pentane washings were removed via cannula
filtration, and the solid washed with Et2O at -10 °C (3 x
50 cm3) . The resultant orange powder was dried in-vacuo
and isolated in the glovebox. Yield 2.68 g, 88 %. 31P NMR:
6 = 46, 42 ppm (1:1 ratio), essentially phosphorus pure.
FW = 1047.73.
Preparation of 1,3-bis- (di-1-adamantylphosphino)propane
palladium (dba)
As above, except using ligand (1.96 g, 3.04 mmol) and
palladium dba (1.69 g, 3.04 mmol [Pd]) in THF (70 cm3).
After 3 h, the deep red-orange solution was fairly turbid
in appearance; an additional 50 cm3 THF was added to
further dissolve the product. The reaction was worked-up
as above, except the EtaO washing was performed at ambient
temperature. The solid was isolated in the glovebox as an
orange powder. Yield 2.08 g, 69 %. 31P NMR: 6 = 42, 38 ppm
(1:1 ratio, noisy). FW = 985.66.
Also see "Studies on the Palladium Catalysed Methoxycarbonylation
of Ethene", thesis submitted to the
University of Durham by G.R. Eastham (1998), for details
on the preparation of L2Pd(dba) complexes.
Example 35
Preparation of methyl propanoate from ethylene, carbon
monoxide and methanol catalysed by a compound of the
present invention
The continuous process exemplified involved the reaction
of purified streams of carbon monoxide, ethylene and
methanol in the liquid phase, in the presence of a
catalyst system, to generate the desired product, methyl
propanoate.
The reaction was carried out at 100°C and at 12 barg
pressure in the reactor vessel.
The catalyst system was made up of three components, being
a palladium salt, a phosphine ligand and an acid. The
three catalyst components, when combined together and
dissolved in the reaction mixture, constitute the reaction
catalyst or catalyst system, a homogeneous catalyst, which
converted dissolved reactants to the product methyl
propanoate in the liquid phase.
During continuous operation, the catalyst decomposed at a
slow but steady rate, and was replaced by adding fresh
catalyst, or the rate of generation of the product, methyl
propanoate reduces.
The reactor vessel was fitted with an agitator, and also a
means of re-circulating the unreacted gas that collected
in the upper headspace area of the reactor. The unreacted
gas from the reactor vessel headspace, which was made up
of a mixture of ethylene and carbon monoxide, was returned
continuously to the reactor via an entry pipe at the base,
such that the gas passed up through the reaction mixture
continuously.
Upon entering into the reactor vessel the gas was
dispersed by the agitator into fine bubbles. In this way
the ethylene and carbon monoxide were dissolved in the
reaction mix.
Fresh ethylene and carbon monoxide gases were added to the
re-circulating gas to make up for the amount of the two
gases that have been used up by the reaction. Fresh
methanol was also added continuously to the reactor
vessel, in order to replace the methanol that has been
used up in the reaction.
The reactor vessel held the bulk liquid reaction mixture,
along with the three components of the homogeneous
catalyst, being a palladium salt, a phhosphine ligand, and
a sulphonic acid.
In order to recover the product methyl propanoate, a
stream of reaction mixture was passed continuously out of
the reactor and into the distillation column.
The distillation column, being a single stage 'flash' type
distillation column, provided a means of separating a
fraction of the methyl propanoate and methanol components
of the reaction mixture from the non-volatile dissolved
catalyst components. This was achieved by vaporising a
fraction of the reaction mixture as it passed through the
flash column. The part of the reaction mixture which
remained as liquid after passing through the flash column,
and which still contained useful catalyst components, was
returned to the reactor vessel so that the catalyst
components could take part in the on-going reaction.
If the methyl propanoate product was required free of
methanol, a second distillation column was required. In
this case, the vapour stream from the flash column, which
is a mixture of methyl propanoate and methanol was passed
into the second distillation column, where the pure methyl
propanoate was generated as the heavier product, and taken
off from the base of the column. A low boiling mixture of
methanol and methyl propanoate was generated as the light
product, and was removed continuously from the top of the
MeP purification column. In order to utilise the methanol
as efficiently as possible in the process, the low boiling
mixture of methanol and methyl propanoate was returned
continuously to the reactor vessel.
135.
After start up of the continuous reactor unit, when the
desired rate of generation of methyl propanoate had been
achieved, a process of gradual reduction of the feed rates
of the catalyst components was undertaken.
In order to sustain the rate of generation of methyl
propanoate it was necessary to continuously replace the
palladium catalyst component which was lost to
decomposition with fresh palladium at a rate which
balanced the rate of loss.
This led to the situation where the standing
concentrations of catalyst components became constant for
a given rate of generation of methyl propanoate, and just
able to sustain flow sheet reaction rate, as indicated by
constant concentrations of carbon monoxide and ethylene in
the headspace area of the reactor vessel. This was called
the balance point, because under these conditions the rate
of palladium decomposition was balanced exactly by the
rate of addition of fresh palladium.
From the rate of addition of fresh palladium catalyst
component under balance point conditions, the palladium
turnover number (TON) was calculated. This is defined as
the number of mol of methyl propanoate generated per hour,
for each mol of palladium consumed by the decomposition
process per hour.
Upon reaching a steady rate at a pre-determined set of
control conditions, the instantaneous values of all of the
variables were recorded, and used as representative data
to show the performance of the process under the
conditions in use at the time.
To gather data on the effect of levels of phosphine ligand
and acid present in the reaction mixture on palladium
turnover number, all variables were held constant except
the background levels of ligand and acid in the reaction
mixture. These levels were changed by making small
additions of these compounds to the reaction vessel via a
dedicated tank and pumping system. The additions were
then followed by careful adjustment of the catalyst
solution feed rate to re-establish the balance position.
The experimental design was such that after collecting
each new set of balance point data, the system was
returned to a previous set of conditions to check for any
drifting of performance before moving on to the next set
of experimental conditions.
In this way, comparative sets of results were drawn up
which showed clearly the changes to catalyst stability
that were caused by the variations in the background
levels of phosphine ligand and acid levels.
The amount of palladium in the feed to the reactor is
critical to calculation of. turnover number results.
Assurance on the rate of fresh catalyst being fed to the
system was provided by analysis of each batch of catalyst
prior to transfer to the catalyst feed tanks for palladium
content. Further assurance was gained by determination of
the actual feed rate of catalyst from timing of the fall
in the level in a burette, which is part of the catalyst
feed system.
Table 9 shows the effect on palladium turnover number
(TON) when increasing the acid:ligand ratio and the
ligand:metal ratio.
In this Example, the acid used was methanesulphonic acid,
the bidentate phosphine ligand was 1,2-bis-
(ditertbutylphosphinomethyl) benzene, and the palladium
compound was tri (dibenzylideneacetone) dipalladium.
(Table Removed)
Further trends are seen in Figures 1-3 of the accompanying
figures.
Figure 1 shows TON versus acid:ligand mol ratio. Clearly,
as the acid:ligand ratio increases above about 10, there
is a large increase in TON for this particular catalyst
system.
Figure 2 shows TON versus amount of methanesulphonic acid
present free in the reactor. Clearly, as the level of
acid increases, there is a large increase in TON for this
particular catalyst system.
Figure 3 shows Pd amount in solution versus amount of
methanesulphonic acid. Clearly, as the level of acid
increases, there is a decrease in the amount of Pd in
solution for this particular catalyst system, whilst the
reaction rate remains constant. Therefore, working at
these elevated acid levels, reaction rates can be
maintained even as the palladium levels decrease. The
advantages in view of the relative cost of the palladium
component of the catalyst system is clear.
Although some preferred embodiments have been shown and
described, it will be appreciated by those skilled in the
art that various changes and modifications might be made
without departing from the scope of the present invention,
as defined in the appended claims.
Attention is directed to all papers and documents which
are filed concurrently with or previous to this
specification in connection with this application and
which are open to public inspection with this
specification, and the contents of all such papers and
documents are incorporated herein by reference.
All of the features disclosed in this specification
(including any accompanying claims, abstract and
drawings) , and/or all of the steps of any method or
process so disclosed, may be combined in any combination,
except combinations where at least some of such features
and/or steps are mutually exclusive.
Each feature disclosed in this specification (including
any accompanying claims, abstract and drawings) may be
replaced by alternative features serving the same,
equivalent or similar purpose, unless expressly stated
otherwise. Thus, unless expressly stated otherwise, each
feature disclosed is one example only of a generic series
of equivalent or similar features.
The invention is not restricted to the details of the
foregoing embodiment (s). The invention extends to any
novel one, or any novel combination, of the features
disclosed in this specification (including any
accompanying claims, abstract and drawings), or to any
novel one, or any novel combination, of the steps of any
method or process so disclosed.







We claim:
1. A catalyst system capable of catalysing the
carbonylation of an ethylenically unsaturated
compound, which system is obtainable by combining:
a) a metal of Group VIB or Group VIIIB or a compound thereof,
b) a bidentate phosphine, arsine, or stibine ligand, and
c) an acid,
wherein the carbonylation is carried out at between -10 to 150°C and a partial pressure of between 0.80 x 105Nm-2 - 90 x 105Nm-2 and
wherein said ligand is present in at least a 2:1 molar excess compared to said metal or said metal in said metal compound, and that said acid is present in the range greater than 5:1 to 95:1 molar excess compared to said ligand; or
wherein the ratio of said ligand to said metal or said metal in said metal compound is in the range 5:1 to 750:1, and that said acid is present at a greater than 2:1 molar excess compared to said ligand.
2. The catalyst system as claimed in claim 1, wherein the
ratio of said ligand to said metal is in the range 5:1
to 750:1.
3. The catalyst system as claimed in claim 1, wherein the ratio of said ligand to said metal is in the range 10:1 to 500 :1.
4. The catalyst system as claimed in claim 1, wherein the
ratio of said acid to said ligand is in the range 5:1
to 95:1.
5. The catalyst system as claimed in claim 1, wherein the
molar ratio of said acid to said metal is in the range
10:1 to 75000:1.
6. The catalyst system as claimed in any preceding
claims, wherein said ligand is a bidentate phosphine
ligand.
7. The catalyst system as claimed in any preceding
claims, wherein said ligand is of general formula (I)
(Formula Removed)
wherein:
Ar is a bridging group comprising an optionally substituted aryl moiety to which the phosphorus atoms are linked on available adjacent carbon atoms;
A and B each independently represent lower alkylene;
K, D, E and Z are substituents of the aryl moiety (Ar) and each independently represent hydrogen, lower alkyl, aryl, Het, halo, cyano, nitro, OR19, OC(O)R20, C(O)R21, C(O)OR22, NR23R24, C(O)NR25R26, C(S)R25R26, SR27, C(O)SR27, or -J-Q3(CR13(R14) (R15) CR1S (R17) (R18) where J represents lower alkylene; or two adjacent groups selected from K, Z, D and E together with the carbon
atoms of the aryl ring to which they are attached form a further phenyl ring, which is optionally substituted by one or more substituents selected from hydrogen, lower alkyl, halo, cyano, nitro, OR19, OC(O)R20, C(O)R21, C(O)OR22, NR23R24, C(O)NR25R2G, C(S)R2bR26, SR27 or C(O)SR27;
R13 to R18 each independently represent lower alkyl, aryl, or Het;
R19 to R27 each independently represent hydrogen, lower alkyl, aryl or Het;
R1 to R12 each independently represent lower alkyl, aryl, or Het;
Q1, Q2 and Q3 (when present) each independently represent phosphorus, arsenic or antimony and in the latter two cases references to phosphine or phosphorus above are amended accordingly, with preferably both Q' and Q2 representing phosphorus, more preferably all of Q1, Q2 and Q3 (when present) representing phosphorus.
8. A catalyst system as claimed in claim 7, wherein at least one (CRxRyRz) group attached to Q1 and/or Q2, i.e. CR1R2R3, CR4R5R6, CR7R8R9, CR10R11R12, CR13R14Rlb, or CR16R17R18, is represented by the group (Ad) wherein:
Ad each independently represent an optionally substituted adamantyl or congressyl radical bonded to the phosphorus atom via any one of its tertiary carbon atoms, the said optional substitution being by one or more substituents selected from hydrogen, lower alkyl, halo, cyano, nitro, OR19, OC(O)R20, C(O)R2], C(O)OR22, NR23R24, C(O)NR25 R26, C(S)R25R26, SR27 or C(O)SR2/; or both (CRxRyRz) groups attached to either or both Q1
and/or Q2, or Q3 (if present) together with either Q1 or Q2 (or Q3) as appropriate, form an optionally substituted 2-phospha-tricyclo[3.3.1.l{3,7}]decyl group or derivative thereof, or form a ring system of formula
(Formula Removed)

wherein
R49, and R54, each independently represent hydrogen,
lower alkyl or aryl;
R50 to R53, when present, each independently represent hydrogen, lower alkyl, aryl or Het; and
Y represents oxygen, sulfur or N-R5b; and R5b, when present, represents hydrogen, lower alkyl or aryl.
9. The catalyst system as claimed in either of claims 7 and 8 wherein said ligand is represented as:
(Ad)s(CR7R8R9)TQ2-A- (K, D) Ar (E, Z) -B-Q1 (Ad)u(CRXR2R3)v
wherein Ar, A, B, K, D, E and Z, Q1, Q2, and Q3, and R1 to R27 are as defined in claim 11 except that K, D, E and Z may represent -J-Q3 (Ad)W(CR13 (R14) (R15)x instead of -J-Q3(CR13(R14) (R15))CR16(R17) (R18) and Ad is as defined in claim 11,
S & U = 0, 1 or 2 provided that S + U ≥ 1 ; T & V = 0, 1 or 2 provided that T + V ≤ 3;
W & X = 0, 1 or 2.
10. The catalyst system as claimed in any of claims 1 to 6 wherein said ligand is of general formula (III) :
(Formula Removed)

wherein:
A1 and A2, and A3, A4 and Ab (when present), each independently represent lower alkylene;
K1 is selected from the group consisting of hydrogen, lower alkyl, aryl, Het, halo, cyano, nitro, -OR19, OC(O)R20, -C(O)R21, -C(O)OR22, -N(R23)R24, -C (O) N (R2b) R26 , -C(S) (R27)R28, -SR29, -C(O)SR30, -CF3 or -A3-Q3(Xb) X6;
D1 is selected from the group consisting of hydrogen, lower alkyl, aryl, Het, halo, cyano, nitro, -OR19, OC(O)R20, -C(O)R21, -C(O)OR22, -N(R23)R2, -C (O) N (R2h) R26 , -C(S) (R27)R28, -SR29, -C(O)SR30, -CF3 or -A4-Q4(X7)X8;
E1 is selected from the group consisting of hydrogen, lower alkyl, aryl, Het, halo, cyano, nitro, -OR'9, OC(O)R20, -C(O)R21, -C(O)OR22, -N(R23)R24, -C(O)N(R2h)R26, -C(S) (R27)R28, -SR29, -C(O)SR30, -CF3 or -Ab-Q5(X9)X10;
or both D1 and E1 together with the carbon atoms of the cyclopentadienyl ring to which they are attached form an optionally substituted phenyl ring:
X1 represents CR1(R2) (R3) , congressyl or adamantyl, X2 represents CR4(R5) (R6) , congressyl or adamantyl, or X1 and X2 together with Q2 to which they are attached form an optionally substituted 2-phospha-tricyclo[3.3.1.l{3,7} ] decyl group or derivative thereof, or X1 and X2 together with Q2 to which they are attached form a ring system of formula Ilia
(Formula Removed)

X3 represents CR7(R8) (R9) , congressyl or adamantyl, X4 represents CR10 (R11) (R12) , congressyl or adamantyl, or X3 and X4 together with Q1 to which they are attached form an optionally substituted 2-phospha-tricyclo[3.3.1.l{3,7}]decyl group or derivative thereof, or X3 and X4 together with Q1 to which they are attached form a ring system of formula IIIb
(Formula Removed)

X5 represents CR13 (R14) (R15), congressyl or adamantyl, X6 represents CR16 (R17) (R18), congressyl or adamantyl, or X5 and X6 together with Q3 to which they are
attached form an optionally substituted 2-phospha-tricyclo[3.3.1.l{3,7}]decyl group or derivative thereof, or X5 and X6 together with Q3 to which they are attached form a ring system of formula IIIc
(Formula Removed)

X7 represents CR31(R32) (R33), congressyl or adamantyl, X8 represents CR34(R35) (R36), congressyl or adamantyl, or X7 and X8 together with Q4 to which they are attached form an optionally substituted 2-phospha-tricyclo[3.3.1.l{3,7} ] decyl group or derivative thereof, or X7 and X8 together with Q4 to which they are attached form a ring system of formula IIId
(Formula Removed)

X9 represents CR37 (R38) (R39) , congressyl or adamantyl, X10 represents CR40 (R41) (R42) , congressyl or adamantyl, or X9 and X10 together with Q5 to which they are attached form an optionally substituted 2-phospha-tricyclo[3.3.1.1.{3 , 7}] decyl group or derivative thereof, or X9 and X10 together with Q5 to which they are attached form a ring system of formula IIIe
(Formula Removed)

Q1 and Q2, and Q3, Q4 and Q5 (when present) , each independently represent phosphorus, arsenic or antimony;
M represents a Group VIB or VIIIB metal or metal cation thereof;
Lx represents an optionally substituted cyclopentadienyl, indenyl or aryl group;
L2 represents one or more ligands each of which are independently selected from hydrogen, lower alkyl, alkylaryl, halo, CO, P(R43) (R44)R45 or N(R46) (R47)R48;
R1 to R18 and R31 to R42, when present, each independently represent hydrogen, lower alkyl, aryl, halo or Het;
R19 to R30 and R43 to R48, when present, each independently represent hydrogen, lower alkyl, aryl or Het;
R49, R54 and R55, when present, each independently represent hydrogen, lower alkyl or aryl;
R50 to R53, when present, each independently represent hydrogen, lower alkyl, aryl or Het;
Y1, Y2, Y3, Y4 and Y5, when present, each independently represent oxygen, sulfur or N-R55;
n = 0 or 1;
and m = 0 to 5;
provided that when n = 1 then m equals 0, and when n equals 0 then m does not equal 0.
11. The catalyst system as claimed in claim 10, wherein if both K1 represents -A3-Q3(X5)X6 and E1 represents -A5-Q5(X9)X10, then D1 represents -A4-Q4 (X7) X8.
12. The catalyst system as claimed in any of claims 8 to
11, wherein adamantyl represents unsubstituted
adamantyl or adamantyl substituted with one or more
unsubstituted C1-C8 alkyl substituents, or a
combination thereof.
13 . The catalyst system as claimed in any of claims 8 to
12, wherein 2-phospha-adamantyl represents
unsubstituted 2-phospha-adamantyl or 2-phospha-
adamantyl substituted with one or more unsubstituted
C1-C8 alkyl substituents, or a combination thereof.
14. The catalyst system as claimed in any of claims 8 to
13, wherein 2-phospha-adamantyl includes one or more
oxygen atoms in the 2-phospha-adamantyl skeleton.
15. The catalyst system as claimed in any of claims 8 to
14, wherein congressyl represents unsubstituted congressyl.
16. The catalyst system as claimed in any of the preceding claims, wherein the metal or compound thereof is palladium.
17. The catalyst system as claimed in claim 16, wherein the palladium is in the metal form.
18. The catalyst system as claimed in any of the preceding
claims, wherein the catalyst system includes in a liquid reaction medium a polymeric dispersant dissolved in a liquid carrier, said polymeric dispersant being capable of stabilising a colloidal suspension of particles of the Group VI or VIIIB metal or metal compound of the catalyst system within the liquid carrier.

Documents:

4679-delnp-2006-Abstract (01-05-2012).pdf

4679-delnp-2006-abstract.pdf

4679-delnp-2006-Claims (01-05-2012).pdf

4679-DELNP-2006-Claims-(28-03-2011).pdf

4679-delnp-2006-claims.pdf

4679-DELNP-2006-Correspondence Others-(28-03-2011).pdf

4679-delnp-2006-correspondence-others.pdf

4679-delnp-2006-description (complete).pdf

4679-delnp-2006-drawings.pdf

4679-delnp-2006-Form-1 (01-05-2012).pdf

4679-DELNP-2006-Form-1-(28-03-2011).pdf

4679-delnp-2006-form-1.pdf

4679-DELNP-2006-Form-13-(28-03-2011).pdf

4679-delnp-2006-form-18.pdf

4679-delnp-2006-Form-2 (01-05-2012).pdf

4679-DELNP-2006-Form-2-(28-03-2011).pdf

4679-delnp-2006-form-2.pdf

4679-DELNP-2006-Form-3-(28-03-2011).pdf

4679-delnp-2006-form-3.pdf

4679-DELNP-2006-Form-5-(28-03-2011).pdf

4679-delnp-2006-form-5.pdf

4679-delnp-2006-pct-101.pdf

4679-delnp-2006-pct-105.pdf

4679-delnp-2006-pct-202.pdf

4679-delnp-2006-pct-210.pdf

4679-delnp-2006-pct-220.pdf

4679-delnp-2006-pct-237.pdf

4679-delnp-2006-pct-301.pdf

4679-delnp-2006-pct-304.pdf

4679-delnp-2006-pct-308.pdf

4679-delnp-2006-pct-332.pdf

4679-delnp-2006-pct-401.pdf

4679-delnp-2006-pct-402.pdf

4679-delnp-2006-pct-409.pdf

4679-delnp-2006-pct-416.pdf

4679-delnp-2006-pct-424.pdf

4679-DELNP-2006-Petition 137-(28-03-2011).pdf


Patent Number 252714
Indian Patent Application Number 4679/DELNP/2006
PG Journal Number 22/2012
Publication Date 01-Jun-2012
Grant Date 28-May-2012
Date of Filing 14-Aug-2006
Name of Patentee LUCITE INTERNATIONAL UK LIMITED
Applicant Address QUEENS GATE, 15-17 QUEENS TERRACE, SOUTHAMPTON, HAMPSHIRE SO 14 BP, UK
Inventors:
# Inventor's Name Inventor's Address
1 TINDALE, NEIL WILTON CENTRE, WILTON, REDCAR, TS10 4RF, UK
2 EASTHAM, GRAHAM WILTON CENTRE, WINTON, REDCAR, TS10 4RF, UK
PCT International Classification Number B01J 31/24
PCT International Application Number PCT/GB2005/000569
PCT International Filing date 2005-02-17
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 0403592.9 2004-02-18 U.K.