U.S. patent application number 13/901252 was filed with the patent office on 2014-01-02 for processes for the preparation of arylamine compounds.
This patent application is currently assigned to UNIVATION TECHNOLOGIES, LLC. The applicant listed for this patent is Adam M. Johns. Invention is credited to Adam M. Johns.
Application Number | 20140005429 13/901252 |
Document ID | / |
Family ID | 42078991 |
Filed Date | 2014-01-02 |
United States Patent
Application |
20140005429 |
Kind Code |
A1 |
Johns; Adam M. |
January 2, 2014 |
Processes for the Preparation of Arylamine Compounds
Abstract
A process for the preparation of N-arylamine compounds, the
process including: reacting a compound having an amino group with
an arylating compound in the presence of a base and a transition
metal catalyst under reaction conditions effective to form an
N-arylamine compound; wherein the transition metal catalyst
comprises a complex of a Group 8-10 metal and at least one
chelating ligand comprising
(R)--(--)-1-[(S)-2-dicyclohexylphosphino]-ferrocenyl]ethyldi-t-butylphosp-
hine.
Inventors: |
Johns; Adam M.; (Burbank,
CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Johns; Adam M. |
Burbank |
CA |
US |
|
|
Assignee: |
UNIVATION TECHNOLOGIES, LLC
Houston
TX
|
Family ID: |
42078991 |
Appl. No.: |
13/901252 |
Filed: |
July 12, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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13126202 |
Apr 27, 2011 |
8501659 |
|
|
PCT/US09/61453 |
Oct 21, 2009 |
|
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13901252 |
|
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61198852 |
Nov 10, 2008 |
|
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Current U.S.
Class: |
556/52 |
Current CPC
Class: |
C07C 213/08 20130101;
C07C 209/10 20130101; C07C 213/08 20130101; C07C 209/10 20130101;
B01J 31/2295 20130101; C07C 217/74 20130101; C07C 211/53
20130101 |
Class at
Publication: |
556/52 |
International
Class: |
B01J 31/22 20060101
B01J031/22 |
Claims
1.-15. (canceled)
16. A process for preparing a Group 15 atom and metal catalyst
compound, the process comprising: a) preparing a ligand comprising
an N-aryl amine compound by reacting a compound having an amino
group with an arylating compound in the presence of a base and a
transition metal catalyst under reaction conditions effective to
form an N-aryl amine compound, wherein the transition metal
catalyst is formed by reacting a Group 8 metal catalyst precursor
comprising palladium (II) acetate (Pd(OAc).sub.7) and at least one
chelating ligand comprising
(R)--(--)-1-[(S)-2-[dicyclohexylphosphino]-ferrocenyl]ethyldi-t-butylphos-
phine; and b) combining the ligand prepared in step a) with a
compound represented by the formula M.sup.nX.sub.n where M is a
Group 3 to 14 metal, n is the oxidation state of M, and X is an
anionic group.
17. The process of claim 16, wherein the compound having an amino
group is selected from the group consisting of primary amines,
secondary amines, and combinations thereof.
18. The process of claim 16, wherein the compound having an amino
group comprises at least one of diethylenetriamine,
1,5-diaminopentane, and 2,2'-oxydiethylamine.
19. The process of claim 16, wherein the arylating compound
comprises at least one compound having the formula: ##STR00031##
wherein X is a halogen atom or a sulfur-containing leaving group,
and R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5are independently
selected from the group consisting of H, CN, alkyl, alkoxy, vinyl,
alkenyl, formyl, CF.sub.3, CCl.sub.3, halide, C.sub.6H.sub.5,
amide, acyl, ester, alkoxy, amino, thioalkoxy, phosphino, and
combinations thereof.
20. The process of claim 16, wherein said arylating compound
comprises at least one of 2,3,4,5,6-pentamethylbromobenzene and
2,4,6-trimethylbromobenzene.
21. The process of claim 16, wherein the N-aryl amine compound
comprises
N.sup.1-(2,3,4,5,6-pentamethylphenyl)-N.sup.2-(2-(2,3,4,5,6-pentamethylpe-
henylamino)ethyl)ethane-1,2-diamine.
22. The process of claim 16, further comprising combining the Group
15 containing metal catalyst compound with at least one of an
activator and a support material.
23. The process of claim 16, wherein the transition metal catalyst
is present during the reacting at a concentration in the range from
about 0.03 to about 1.0 mole percent, based on a total amount of
the compound having an amino group, the arylating compound, and the
transition metal catalyst.
24. The process of claim 16, further comprising combining the
N-aryl amine compound with a compound represented by the formula
M.sup.nX.sub.n where M is a Group 3 to 14 metal, n is the oxidation
state of M, and X is an anionic group to form a Group 15 containing
metal catalyst compound.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. provisional
application Serial No. 61/198852, filed Nov. 10, 2008, the
disclosure of which is incorporated by reference in its
entirety.
FIELD OF THE INVENTION
[0002] In one aspect, embodiments disclosed herein relate to the
preparation of arylamines In another aspect, embodiments disclosed
herein relate to the preparation of Group 15 atom and metal
catalyst compounds.
BACKGROUND
[0003] N-arylamines compounds are important substructures in
natural products and industrial chemicals, such as pharmaceuticals,
dyes, and agricultural products. N-arylamines are useful for
screening for pharmaceutical and biological activity and in the
preparation of commercial polymers. It would be advantageous to
prepare N-arylamine compounds from arylating compounds such as aryl
halides and/or aryl tosylates because aryl halides are generally
inexpensive and readily available, while aryl tosylates are easily
prepared from phenols. However, to date, methods of producing
N-arylamines are inefficient or economically unattractive. Many
known processes that generate an aryl-nitrogen bond must be
performed under harsh reaction conditions, or must employ activated
substrates which are sometimes not available. Examples of
procedures that generate aryl amine compounds include nucleophilic
substitution of aryl precursors and synthesis of aryl amines via
copper-mediated Uhlmann condensation reactions.
[0004] The commercialization of metallocene polyolefin catalysts
has led to widespread interest in the design and preparation of
other catalysts and catalyst systems, particularly for use in
economical gas and slurry phase processes. Anionic, multidentate
heteroatom ligands have received attention in polyolefins
catalysis. Notable classes of bidentate anionic ligands which form
active polymerization catalysts include N--N.sup.- and N--O.sup.-
ligand sets. Examples of these types of catalysts include
amidopyridines and polyolefin catalysts based on
hydroxyquinolines.
[0005] U.S. Pat. No. 5,576,460 (the '460 patent) discloses two
synthesis routes to preparing arylamine compounds. The first route
includes reaction of a metal amide comprising a metal selected from
the group consisting of tin, boron, zinc, magnesium, indium and
silicon, with an aromatic compound comprising an activated
substituent in the presence of a transition metal catalyst to form
an arylamine The second route utilizes an amine rather than a metal
amide. The '460 patent teaches that this reaction be conducted at a
temperature of less than about 120.degree. C. and is drawn to the
use of the arylamine as an intermediate in pharmaceutical and
agricultural applications.
[0006] U.S. Pat. No. 5,929,281 discloses the preparation of
heterocyclic aromatic amines in the presence of a catalyst system
comprising a palladium compound and a tertiary phosphine and the
preparation of arylamines in the presence of a catalyst system
comprising a palladium compound and a trialkylphosphine.
[0007] U.S. Pat. No. 3,914,311 discloses a low temperature method
of preparing an arylamine by the reaction of an amine with an
aromatic compound having a displaceable activated substituent at
temperatures as low as 25.degree. C. in the presence of nickel
catalyst and a base.
[0008] Other patents discussing N-arylamine compounds may include
U.S. Pat. Nos. 6,235,938 and 6,518,444, among others, as well as
references such as, Shen, Q., Shekhar, S, Stambuli, J. P., Hartwig,
J. F., Angew. Chem., Int. Ed.; 2005, 44, 1371-1375.
[0009] A need exists for a general and efficient process of
synthesizing N-arylamine compounds from readily available arylating
compounds. The discovery and implementation of such a method would
simplify the preparation of commercially significant organic N-aryl
amines and would enhance the development of novel polymers and
pharmacologically active compounds.
SUMMARY
[0010] In one aspect, embodiments disclosed herein relate to a
process for the preparation of N-aryl amine compounds, the process
including: reacting a compound having an amino group with an
arylating compound in the presence of a base and a transition metal
catalyst under reaction conditions effective to form an N-aryl
amine compound; wherein the transition metal catalyst comprises a
complex of a Group 8-10 metal and at least one chelating ligand
comprising
(R)--(--)-1-[(S)-2-dicyclohexylphosphino]-ferrocenyl]ethyldi-t-butylphosp-
hine.
[0011] In another aspect, embodiments disclosed herein relate to a
process for preparing a Group 15 atom and metal catalyst compound,
the process including: a) preparing a ligand comprising an N-aryl
amine compound by reacting a compound having an amino group with an
arylating compound in the presence of a base and a transition metal
catalyst under reaction conditions effective to form an N-aryl
amine compound, wherein the transition metal catalyst comprises a
Group 8 metal and at least one chelating ligand comprising
(R)-(+1-[(S)-2-dicyclohexylphosphino]-ferrocenyl]ethyldi-t-butylphosphine-
; and b) combining the ligand prepared in step a) with a compound
represented by the formula M.sup.nX.sub.n where M is a Group 3 to
14 metal, n is the oxidation state of M, and X is an anionic
group.
BRIEF DESCRIPTION OF THE DRAWING
[0012] FIG. 1 is a graphical comparison of the performance of
catalysts according to embodiments disclosed herein and comparative
catalysts for the production of N-aryl amines.
DETAILED DESCRIPTION
[0013] Before the present compounds, components, compositions,
and/or methods are disclosed and described, it is to be understood
that unless otherwise indicated this invention is not limited to
specific compounds, components, compositions, reactants, reaction
conditions, ligands, metallocene structures, or the like, as such
may vary, unless otherwise specified. It is also to be understood
that the terminology used herein is for the purpose of describing
particular embodiments only and is not intended to be limiting.
[0014] It must also be noted that, as used in the specification and
the appended claims, the singular forms "a," "an" and "the" include
plural referents unless otherwise specified. Thus, for example,
reference to "a leaving group" as in a moiety "substituted with a
leaving group" includes more than one leaving group, such that the
moiety may be substituted with two or more such groups. Similarly,
reference to "a halogen atom" as in a moiety "substituted with a
halogen atom" includes more than one halogen atom, such that the
moiety may be substituted with two or more halogen atoms, reference
to "a substituent" includes one or more substituents, reference to
"a ligand" includes one or more ligands, and the like.
[0015] As used herein, all reference to the Periodic Table of the
Elements and groups thereof is to the NEW NOTATION published in
HAWLEY'S CONDENSED CHEMICAL DICTIONARY, Thirteenth Edition, John
Wiley & Sons, Inc., (1997) (reproduced there with permission
from IUPAC), unless reference is made to the Previous IUPAC form
noted with Roman numerals (also appearing in the same), or unless
otherwise noted.
[0016] In one aspect, embodiments disclosed herein relate to the
preparation of N-aryl amine compounds. In another aspect,
embodiments disclosed herein relate to the preparation of Group 15
atom and metal catalyst compounds.
[0017] Preparation of N-Aryl Amine Ligands (Ligands YLZ and
YL'Z)
[0018] N-aryl amine compounds may be synthesized according to
embodiments disclosed herein from a compound having an amino group,
and an arylating compound. The term "aryl" is defined herein as a
compound whose molecules have the ring structure characteristic of
benzene, naphthalene, phenanthroline, anthracene, heterocyclic, and
the like. "Arylating compound" is defined as a compound which
provides an aryl substituent in an organic reaction. "N-Aryl amine
compounds" are those compounds in which a nitrogen atom of the
compound is substituted with an aryl group.
[0019] The reaction may be performed in the presence of a base and
a Group 8-10 transition metal catalyst. One example of a reaction
between an arylating compound and an amine to produce an N-aryl
amine compound may be represented by reaction (I):
##STR00001##
[0020] Briefly, in reaction (I), an arylating compound is reacted
with an amine compound in the presence of a base and a Group 8-10
transition metal (M) complex including a chelating ligand (LL) to
form an N-aryl amine compound. Each of these reactions and their
components are described in more detail below.
[0021] The transition metal catalyst according to embodiments
disclosed herein is a Group 8-10 transition metal complex of
((R)--(--)--1-[(S)-2-dicyclohexylphosphino)-ferrocenyl]ethyldi-t-butylpho-
sphine), herein abbreviated as CyPF-t-Bu. In certain embodiments,
the Group 8-10 transition metal comprises at least one of
palladium, platinum, and nickel. In some embodiments, the Group
8-10 transition metal is palladium. It has been found that the
palladium complex of CyPF-t-Bu may beneficially yield higher
conversions and selectivity than prior palladium catalysts
disclosed for production of N-aryl amine compounds, thus allowing
for efficient production of N-aryl amine compounds, an important
class of compounds which are particularly significant in the
development of pharmacologically active compounds and processing of
polymers and oligomers.
[0022] N-aryl amine compounds may be synthesized according to
embodiments disclosed herein by reaction of an amine-containing
compound, such as a primary amine or a secondary amine, with an
arylating compound in the presence of a base and a Group 8-10
transition metal complex of CyPF-t-Bu under reaction conditions
effective to form an N-aryl amine compound. CyPF-t-Bu may be
represented by formula (II).
##STR00002##
[0023] The arylating compound used in the process of the present
invention may be any arylating compound of the formula (III):
##STR00003##
[0024] In formula (III), X may be any halide atom (F, Cl, Br, I),
or any sulfur-containing leaving group (e.g., triflate, sulfonate,
tosylate, and the like) known in the art. Chlorides are especially
preferred in the process of the present invention. R.sub.1,
R.sub.2, R.sub.3, R.sub.4, and R.sub.5 are independently selected
from H; CN; alkyl, such as methyl, ethyl, propyl, n-butyl, t-butyl,
and the like; alkoxy, vinyl, alkenyl, formyl; CF.sub.3; CCl.sub.3;
halide, C.sub.6 H.sub.5; amide such as C(O)N(CH.sub.3).sub.2,
C(O)N(CH.sub.2 CH.sub.3).sub.2, C(O)N(CH.sub.2 CH.sub.2
CH.sub.3).sub.2, and the like; acyl, such as C(O)-C.sub.6 H.sub.5,
and the like; ester, amino, thioalkoxy, phosphino, and the like.
Arylating compound may also be a heterocyclic aromatic compound
such as an azole or azole derivative, aryl phosphates, aryl
trifluoroacetates, and the like. Alternatively, the arylating
compound may be the process of claim 1, wherein said arylating
compound any aromatic or heteroaromatic halide, such as an aromatic
or heteroaromatic chloride.
[0025] Preferred arylating compounds used in the process of the
invention may include aryl bromides such as chlorobenzene,
4-chloro-benzonitrile, 4-chloro-t-butyl benzene, 3-chloro-methoxy
benzene, 2-chloro toluene, p-formyl pheryl chloride, p-CF.sub.3
phenyl chloride, p-phenyl phenyl chloride, p-C(O)N(CH.sub.2
CH.sub.3).sub.2 phenyl chloride, and p-C(O)-C.sub.6 H.sub.5 phenyl
chloride.
[0026] In some embodiments, the arylating compound may include at
least one of 2,3,4,5,6-pentamethylbromobenzene (PMBB) and
2,4,6-trimethylbromobenzene (TMBB). In some embodiments, the
arylating compound may include 2,3,4,5,6-pentamethylbromobenzene.
In other embodiments, the arylating compound may include
2,4,6-trimethylbromobenzene.
[0027] According to the method of the invention, amine-containing
compounds include primary amine (e.g., R or R' is hydrogen) or
secondary amine compounds (e.g., R and R' are not H). Examples of
useful primary amines include aniline (NH.sub.2 Ph) and aminobutane
(NH.sub.2 Bu). Examples of useful secondary amines include
morphiline (C.sub.4 H.sub.9 NO) and piperidine (C.sub.5 H.sub.11
N). Other useful amines may include diethylenetriamene, 1,5
diaminopentane, and 2,2'-oxydiethylamine, among others. Such amines
may be used alone or in combination.
[0028] The base shown in Scheme I is required for the process of
the invention. Any base may be used so long as the process of the
invention proceeds to the N-aryl amine product. It may be important
in this regard that the base does not displace all of the chelating
ligands on the catalyst. Nuclear magnetic resonance, infrared, and
Raman spectroscopies, for example, are useful in determining
whether the chelating ligands remain bonded to the Group 8-10 metal
or whether the ligands have been displaced by the base.
[0029] Non-limiting examples of suitable bases include alkali metal
hydroxides, such as sodium and potassium hydroxides; alkali metal
alkoxides, such as sodium t-butoxide; metal carbonates, such as
potassium carbonate, cesium carbonate, and magnesium carbonate;
phosphates; alkali metal aryl oxides, such as potassium phenoxide;
alkali metal amides, such as lithium amide; tertiary amines, such
as triethylamine and tributylamine; (hydrocarbyl)ammonium
hydroxides, such as benzyltrimethylammonium hydroxide and
tetraethylammonium hydroxide; and diaza organic bases, such as
1,8-diazabicyclo[5.4.0]-undec-7-ene and
1,8-diazabicyclo-[2.2.2.]-octane. Preferably, the base is an alkali
hydroxide or alkali alkoxide, more preferably, an alkali alkoxide,
and most preferably, an alkali metal C.sub.1-10 alkoxide.
[0030] The quantity of base which is used can be any quantity which
allows for the formation of the N-aryl amine product. Preferably,
the molar ratio of base to arylating compound ranges from about 1:1
to about 3:1, and more preferably between about 1:1 and 2:1.
[0031] In one particular embodiments, the amine compound may be
diethylenetriamine and the arylating compound may be
2,3,4,5,6-pentamethylbromobenzene to form
N.sup.1-(2,3,4,5,6-pentamethylphenyl)-N.sup.2-(2-(2,3,4,5,6-pentamethylph-
enylamino)ethyl)ethane-1,2-diamine, where the reaction, represented
by formula (IV), is performed in the presence of the above
described palladium complex with CyPF-t-Bu as the ligand (L).
##STR00004##
[0032] The transition metal catalyst may be synthesized first and
thereafter employed in the arylation process. Alternatively, the
catalyst can be prepared in situ in the arylation reaction mixture.
If the latter is used, then a palladium catalyst precursor compound
and the chelating ligand (CyPF-tBu) are independently added to the
reaction mixture wherein formation of the transition metal catalyst
occurs in situ. Suitable precursor compounds include alkene and
diene complexes of palladium, preferably, di(benzylidene)acetone
(dba) complexes of palladium, as well as, monodentate phosphine
complexes of the palladium, and palladium carboxylates. In the
presence of the chelating ligand, in situ formation of the
transition metal catalyst occurs. Non-limiting examples of suitable
precursor compounds include [bis-di(benzylidene)acetone]palladium
(0), tetrakis-(triphenylphosphine)-palladium (0),
tris-[di(benzylidene)acetone]palladium (0), tris-[di(benzylidene)
acetone]-dipalladium (0), palladium acetate, and the analogous
complexes of iron, cobalt, nickel, ruthenium, rhodium, osmium,
iridium, and platinum. Any of the aforementioned catalyst
precursors may include a solvent of crystallization. Group 8-10
metals supported on carbon, preferably, palladium on carbon, can
also be suitably employed as a precursor compound. In certain
embodiments, the catalyst precursor compound is palladium
acetate.
[0033] The quantity of transition metal catalyst which is employed
in the process of this invention is any quantity which promotes the
formation of the N-aryl product. Generally, the quantity is a
catalytic amount, which means that the catalyst is used in an
amount which is less than stoichiometric relative to the
unsaturated organic sulfonate. Typically, the transition metal
catalyst ranges from about 0.01 to about 20 mole percent, based on
the number of moles of the compound having at least one unsaturated
nitrogen atom used in the reaction. Preferably, the quantity of
transition metal catalyst ranges from about 1 to about 10 mole
percent, and more preferably from about 3 to about 8 mole percent,
based on the moles of the unsaturated nitrogen-containing
compound.
[0034] The process described herein may be conducted in any
conventional reactor designed for catalytic processes. Continuous,
semi-continuous, and batch reactors can be employed. If the
catalyst is substantially dissolved in the reaction mixture as in
homogeneous processes, then batch reactors, including stirred tank
and pressurized autoclaves, can be employed. If the catalyst is
anchored to a support and is substantially in a heterogeneous
phase, then fixed-bed and fluidized bed reactors can be used. In
the typical practice of this invention the compound having an amino
group, arylating compound, base, and catalyst are mixed in batch,
optionally with a solvent, and the resulting mixture is maintained
at a temperature and pressure effective to prepare the N-arylated
product.
[0035] Any solvent can be used in the process of the invention
provided that it does not interfere with the formation of the
N-aryl amine product. Both aprotic and protic solvents and
combinations thereof are acceptable. Suitable aprotic solvents
include, but are not limited to, aromatic hydrocarbons, such as
toluene and xylene, chlorinated aromatic hydrocarbons, such as
dichlorobenzene, and ethers, such as tetrahydroturan. Suitable
protic solvents include, but are not limited to, water and
aliphatic alcohols, such as ethanol, isopropanol, and cyclohexonol,
as well as glycols and other polyols. The amount of solvent which
is employed may be any amount, preferably an amount sufficient to
solubilize, at least in part, the reactants and base. A suitable
quantity of solvent typically ranges from about 1 to about 100
grams solvent per gram reactants. Other quantities of solvent may
also be suitable, as determined by the specific process conditions
and by the skilled artisan.
[0036] Catalysts may be used to prepare N-aryl amines according to
embodiments disclosed herein at any effective amount. In some
embodiments, the transition metal catalyst is present during the
arylation reaction at a concentration in the range from about 0.01
to about 1.25 mole percent, based on a total amount of the compound
having an amino group, the arylating compound, and the transition
metal catalyst. In other embodiments, the transition metal catalyst
is present during the arylation reaction at a concentration in the
range from about 0.03 to about 1.0 mole percent, based on a total
amount of the compound having an amino group, the arylating
compound, and the transition metal catalyst; from about 0.03 to
about 0.5 mole percent, based on a total amount of the compound
having an amino group, the arylating compound, and the transition
metal catalyst in other embodiments; and from about 0.05 to about
0.1 mole percent, based on a total amount of the compound having an
amino group, the arylating compound, and the transition metal
catalyst in yet other embodiments.
[0037] Generally, the reagents may be mixed together or added to a
solvent in any order. Air is preferably removed from the reaction
vessel during the course of the reaction, however this step is not
always necessary. If it is desirable or necessary to remove air,
the solvent and reaction mixture can be sparged with a non-reactive
gas, such as nitrogen, helium, or argon, or the reaction may be
conducted under anaerobic conditions. The process conditions can be
any operable conditions which yield the desired N-aryl product.
Beneficially, the reaction conditions for this process are mild.
For example, a preferred temperature for the process of the present
invention ranges from about ambient, taken as about 22.degree. C.,
to about 150.degree. C., and preferably, from about 80.degree. C.
to about 110.degree. C. The process may be run at subatmospheric
pressures if necessary, but typically proceeds sufficiently well at
about atmospheric pressure. The process is generally run for a time
sufficient to convert as much of the unsaturated
nitrogen-containing compound to product as possible. Typical
reaction times range from about 30 minutes to about 24 hours, but
longer times may be used if necessary.
[0038] The N-arylated amine product can be recovered by
conventional methods known to those skilled in the art, including,
for example, distillation, crystallization, sublimation, and gel
chromatography. The yield of product will vary depending upon the
specific catalyst, reagents, and process conditions used. For the
purposes of this invention, "yield" is defined as the mole
percentage of N-aryl amine product recovered, based on the number
of moles of unsaturated nitrogen-containing compound employed.
Typically, the yield of N-aryl amine product is greater than about
25 mole percent. Preferably, the yield of N-aryl amine product is
greater than about 60 mole percent, and more preferably, greater
than about 80 mole percent.
Group 15 Atom and Metal Catalyst Compound
[0039] The Group 15 atom and metal catalyst compounds, which may be
prepared by methods disclosed herein, generally include a Group 3
to 14 metal atom, preferably a Group 3 to 7, more preferably a
Group 4 to 6, and even more preferably a Group 4 metal atom, bound
to at least one leaving group and also bound to at least two Group
15 atoms, at least one of which is also bound to a Group 15 or 16
atom through another group. The Group 15 atoms of the catalyst
compound are also bound to a Group 15 or 16 atom through another
group which may be a C.sub.1 to C.sub.20 hydrocarbon group, a
heteroatom containing group, silicon, germanium, tin, lead, or
phosphorus, wherein the Group 15 or 16 atom may also be bound to
nothing or a hydrogen, a Group 14 atom containing group, a halogen,
or a heteroatom containing group, and wherein each of the two Group
15 atoms are also bound to a cyclic group and may optionally be
bound to hydrogen, a halogen, a heteroatom or a hydrocarbyl group,
or a heteroatom containing group.
[0040] In another embodiment, the Group 15 containing metal
catalyst compound, prepared by the method of the present invention
is represented by the formulae:
##STR00005##
wherein: M is a Group 3 to 12 transition metal or a Group 13 or 14
main group metal, preferably a Group 4, 5, or 6 metal, and more
preferably a Group 4 metal, and most preferably zirconium, titanium
or hafnium; each X is independently a leaving group, preferably, an
anionic leaving group, and more preferably hydrogen, a hydrocarbyl
group, a heteroatom or a halogen, and most preferably an alkyl; y
is 0 or 1 (when y is 0 group L' is absent); n is the oxidation
state of M, preferably +3, +4, or +5, and more preferably +4; m is
the formal charge of the YLZ or the YL'Z ligand, preferably 0, -1,
-2 or -3, and more preferably -2; L is a Group 15 or 16 element,
preferably nitrogen; L' is a Group 15 or 16 element or Group 14
containing group, preferably carbon, silicon or germanium; Y is a
Group 15 element, preferably nitrogen or phosphorus, and more
preferably nitrogen; Z is a Group 15 element, preferably nitrogen
or phosphorus, and more preferably nitrogen; R.sup.1 and R.sup.2
are independently a C.sub.1 to C.sub.1 hydrocarbon group, a
heteroatom containing group having up to twenty carbon atoms,
silicon, germanium, tin, lead, or phosphorus, preferably a C.sub.2
to C.sub.20 alkyl, aryl or aralkyl group, more preferably a linear,
branched or cyclic C.sub.2 to C.sub.20 alkyl group, most preferably
a C.sub.2 to C.sub.6 hydrocarbon group; R.sup.3 is absent or a
hydrocarbon group, hydrogen, a halogen, a heteroatom containing
group, preferably a linear, cyclic or branched alkyl group having 1
to 20 carbon atoms, more preferably R.sup.3 is absent, hydrogen or
an alkyl group, and most preferably hydrogen; R.sup.4 and R.sup.5
are independently an alkyl group, an aryl group, substituted aryl
group, a cyclic alkyl group, a substituted cyclic alkyl group, a
cyclic aralkyl group, a substituted cyclic aralkyl group or
multiple ring system, preferably having up to 20 carbon atoms, more
preferably between 3 and 10 carbon atoms, and even more preferably
a C.sub.1 to C20 hydrocarbon group, a C.sub.1 to C.sub.20 aryl
group or a C.sub.1 to C.sub.20 aralkyl group, or a heteroatom
containing group, for example PR.sub.3, where R is an alkyl group,
R.sup.1 and R.sup.2 may be interconnected to each other, and/or
R.sup.4 and R.sup.5 may be interconnected to each other; R.sup.6
and R.sup.2 are independently absent, or hydrogen, an alkyl group,
halogen, heteroatom or a hydrocarbyl group, preferably a linear,
cyclic or branched alkyl group having 1 to 20 carbon atoms, more
preferably absent; and R* is absent, or is hydrogen, a Group 14
atom containing group, a halogen, a heteroatom containing
group.
[0041] By "formal charge of the YLZ or YL'Z ligand" it is meant the
charge of the entire ligand absent the metal and the leaving groups
X.
[0042] By "R.sup.1 and R.sup.2 may also be interconnected" it is
meant that R.sup.1 and R.sup.2 may be directly bound to each other
or may be bound to each other through other groups. By "R.sup.4 and
R.sup.5 may also be interconnected" it is meant that R.sup.4 and
R.sup.5 may be directly bound to each other or may be bound to each
other through other groups.
[0043] An alkyl group may be a linear, branched alkyl radicals, or
alkenyl radicals, alkynyl radicals, cycloalkyl radicals or aryl
radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy
radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl
radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- or
dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,
aroylamino radicals, straight, branched or cyclic, alkylene
radicals, or combination thereof. An aralkyl group is defined to be
a substituted aryl group.
[0044] In a preferred embodiment R.sup.4 and R.sup.5 are
independently a group represented by the following Formula
(VII):
##STR00006##
wherein R.sup.8 to R.sup.12 are each independently hydrogen, a
C.sub.1 to C.sub.40 alkyl group, a halide, a heteroatom, a
heteroatom containing group containing up to 40 carbon atoms,
preferably a C.sub.1 to C.sub.20 linear or branched alkyl group,
preferably a methyl, ethyl, propyl or butyl group, any two R groups
may form a cyclic group and/or a heterocyclic group. The cyclic
groups may be aromatic. In a preferred embodiment R.sup.9, R.sup.16
and R.sup.12 are independently a methyl, ethyl, propyl or butyl
group (including all isomers), in a preferred embodiment R.sup.9,
R.sup.16 and R.sup.12 are methyl groups, and R.sup.8 and R.sup.11
are hydrogen.
[0045] In one particular embodiment, R.sup.4 and R.sup.5 are both a
group represented by the following Formula (VIII):
##STR00007##
[0046] In this embodiment, M is a Group 4 metal, preferably
zirconium, titanium or hafnium, and even more preferably zirconium;
each of L, Y, and Z is nitrogen; each of R.sup.1 and R.sup.2 is
--CH.sub.2--CH.sub.2--; R.sup.3 is hydrogen; and R.sup.6 and
R.sup.7 are absent.
[0047] In a particularly preferred embodiment the Group 15
containing metal catalyst compound, is represented by Compound
(IX), below, where Ph denotes a phenyl group:
##STR00008##
[0048] In another embodiment, R.sup.4 and R.sup.5 are both a group
represented by the following Formula (X):
##STR00009##
[0049] In this embodiment, M is a Group 4 metal, preferably
zirconium, titanium or hafnium, and even more preferably zirconium;
each of L, Y, and Z is nitrogen; each of R.sup.1 and R.sup.2 is
--CH.sub.2--CH.sub.2--; R.sup.3 is hydrogen; and R.sup.6 and
R.sup.2 are absent.
[0050] In a particularly preferred embodiment the Group 15
containing metal catalyst compound, is represented by Compound
(XI), below, where Ph denotes a phenyl group:
##STR00010##
Preparation of the Group 15 Atom and Metal Catalyst Compound
[0051] The Group 15 atom and metal catalyst compounds may be
prepared by reacting the neutral ligand, YLZ or YL'Z, prepared as
described above, with a compound represented by the formula M.sup.n
X.sub.n, as is known in the art. where M is a Group 3 to 14 metal,
n is the oxidation state of M, each X is independently a leaving
group, preferably, an anionic leaving group, and more preferably
hydrogen, a hydrocarbyl group, a heteroatom or a halogen, and most
preferably an alkyl, in a non-coordinating or weakly coordinating
solvent, such as ether, toluene, xylene, benzene, methylene
chloride, and/or hexane or other solvent having a boiling point at
about 20.degree. C. to about 150.degree. C., and preferably
20.degree. C. to 100.degree. C., preferably for 24 hours or more.
When X is a halogen, the mixture is then treated with an excess
(such as four or more equivalents) of a strong base, such as for
example, lithiumdimethylamide (LiN(CH.sub.3).sub.2), or an
alkylating agent, such as for example methyl magnesium bromide in
ether. The magnesium salts, if present, are removed by filtration.
The resulting metal complex is then isolated by standard
techniques. In a preferred embodiment the solvent has a boiling
point above 60.degree. C., such as toluene, xylene, benzene, and/or
hexane. In another embodiment the solvent comprises ether and/or
methylene chloride, either being preferable.
[0052] For example, in some embodiments, the Group 15 atom and
metal catalyst compounds, such as that illustrated in Structure
(XI), may be prepared by reacting the neutral ligand, YLZ or YL'Z,
prepared as described above, with a compound represented by the
formula M.sup.nX.sub.n, where M is Zr, n is the oxidation state of
M, and each X is an anionic group, such as a alkyl.
[0053] As another example, in some embodiments, the Group 15 atom
and metal catalyst compounds, such as that illustrated in Structure
(XI), may be prepared by reacting the neutral ligand, YLZ or YL'Z,
prepared as described above, with a compound represented by the
formula M.sup.nX.sub.n, as is known in the art, where M is a Group
3 to 14 metal, n is the oxidation state of M, each X is an anionic
group, such as benzyl, in a non-coordinating or weakly coordinating
solvent, such as toluene, xylene, benzene, methylene chloride,
and/or hexane or other solvent having a boiling point at about
20.degree. C. to about 150.degree. C., and preferably 20.degree. C.
to 100.degree. C., preferably for one hour or more. The resulting
metal complex can be isolated by removing the solvent and washing
the resultant solid with hexane to yield a powder. In a preferred
embodiment the solvent for the reaction is toluene.
Activators and Activation Methods for Catalyst Compounds
[0054] The Group 15 atom and metal catalyst compounds, prepared
above, are typically combined with an activator compound to yield
compounds having a vacant coordination site that will coordinate,
insert, and polymerize olefin(s). For the purposes of this patent
specification and appended claims, the term "activator" is defined
to be any compound which can activate any one of the catalyst
compounds described above by converting the neutral catalyst
compound to a catalytically active catalyst compound cation.
Non-limiting activators, for example, include alumoxanes, aluminum
alkyls, ionizing activators, which may be neutral or ionic, and
conventional-type cocatalysts.
Alumoxane and Aluminum Alkyl Activators
[0055] In one embodiment, alumoxanes activators are utilized as an
activator in the catalyst composition of the invention. Alumoxanes
are generally oligomeric compounds containing --Al(R)--O--
subunits, where R is an alkyl group. Examples of alumoxanes include
methylalumoxane (MAO), modified methylalumoxane (MMAO),
ethylalumoxane and isobutylalumoxane. Alumoxanes may be produced by
the hydrolysis of the respective trialkylaluminum compound. MMAO
may be produced by the hydrolysis of trimethylaluminum and a higher
trialkylaluminum such as triisobutylaluminum. MMAO's are generally
more soluble in aliphatic solvents and more stable during storage.
There are a variety of methods for preparing alumoxane and modified
alumoxanes, non-limiting examples of which are described in U.S.
Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419,
4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032,
5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529,
5,693,838, 5,731,253, 5,731,451, 5,744,656, 5,847,177, 5,854,166,
5,856,256 and 5,939,346 and European publications EP-A-0 561 476,
EP-B1-0 279 586, EP-A-0 594-218 and EP-B1-0 586 665, and PCT
publications WO 94/10180 and WO 99/15534, all of which are herein
fully incorporated by reference. A another alumoxane is a modified
methyl alumoxane (MMAO) cocatalyst type 3A (commercially available
from Akzo Chemicals, Inc. under the trade name Modified
Methylalumoxane type 3A, covered under patent number U.S. Pat. No.
5,041,584).
[0056] Aluminum alkyl or organoaluminum compounds which may be
utilized as activators include trimethylaluminum, triethylaluminum,
triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and
the like.
Ionizing Activators
[0057] It is within the scope of this invention to use an ionizing
or stoichiometric activator, neutral or ionic, such as tri
(n-butyl) ammonium tetrakis (pentafluorophenyl) boron, a
trisperfluorophenyl boron metalloid precursor or a
trisperfluoronaphtyl boron metalloid precursor, polyhalogenated
heteroborane anions (WO 98/43983), boric acid (U.S. Pat. No.
5,942,459) or combination thereof. It is also within the scope of
this invention to use neutral or ionic activators alone or in
combination with alumoxane or modified alumoxane activators.
[0058] Examples of neutral stoichiometric activators include
tri-substituted boron, tellurium, aluminum, gallium and indium or
mixtures thereof. The three substituent groups are each
independently selected from alkyls, alkenyls, halogen, substituted
alkyls, aryls, arylhalides, alkoxy and halides. Preferably, the
three groups are independently selected from halogen, mono or
multicyclic (including halosubstituted) aryls, alkyls, and alkenyl
compounds and mixtures thereof, preferred are alkenyl groups having
1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms,
alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3
to 20 carbon atoms (including substituted aryls). More preferably,
the three groups are alkyls having 1 to 4 carbon groups, phenyl,
napthyl or mixtures thereof. Even more preferably, the three groups
are halogenated, preferably fluorinated, aryl groups. Most
preferably, the neutral stoichiometric activator is
trisperfluorophenyl boron or trisperfluoronapthyl boron.
[0059] Ionic stoichiometric activator compounds may contain an
active proton, or some other cation associated with, but not
coordinated to, or only loosely coordinated to, the remaining ion
of the ionizing compound. Such compounds and the like are described
in European publications EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495
375, EP-B1-0 500 944, EP-A-0 277 003 and EP-A-0 277 004, and U.S.
Pat. Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025,
5,384,299 and 5,502,124 and U.S. patent application Ser. No.
08/285,380, filed Aug. 3, 1994, all of which are herein fully
incorporated by reference.
[0060] In a preferred embodiment, the stoichiometric activators
include a cation and an anion component, and may be represented by
the following formula:
[0061] The cation component, (L-H).sub.d.sup.+ may include Bronsted
acids such as protons or protonated Lewis bases or reducible Lewis
acids capable of protonating or abstracting a moiety, such as an
akyl or aryl, from the metallocene or Group 15 containing
transition metal catalyst precursor, resulting in a cationic
transition metal species.
[0062] The activating cation (L-H).sub.d.sup.+ may be a Bronsted
acid, capable of donating a proton to the transition metal
catalytic precursor resulting in a transition metal cation,
including ammoniums, oxoniums, phosphoniums, silyliums and mixtures
thereof, preferably ammoniums of methylamine, aniline,
dimethylamine, diethylamine, N-methylaniline, diphenylamine,
trimethylamine, triethylamine, N,N-dimethylaniline,
methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,
p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,
triphenylphosphine, and diphenylphosphine, oxomiuns from ethers
such as dimethyl ether diethyl ether, tetrahydrofuran and dioxane,
sulfoniums from thioethers, such as diethyl thioethers and
tetrahydrothiophene and mixtures thereof. The activating cation
(L-H).sub.d.sup.+ may also be an abstracting moiety such as silver,
carboniums, tropylium, carbeniums, ferroceniums and mixtures,
preferably carboniums and ferroceniums. Most preferably
(L-H).sub.d.sup.+ is triphenyl carbonium.
[0063] The anion component A.sup.d-include those having the formula
[M.sup.k+ Qn].sup.d- where k is an integer from 1 to 3; n is an
integer from 2-6; n-k=d; M is an element selected from Group 13 of
the Periodic Table of the Elements, preferably boron or aluminum,
and Q is independently a hydride, bridged or unbridged
dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted
hydrocarbyl, halocarbyl, substituted halocarbyl, and
halosubstituted-hydrocarbyl radicals, said Q having up to 20 carbon
atoms with the proviso that in not more than 1 occurrence is Q a
halide. Preferably, each Q is a fluorinated hydrocarbyl group
having 1 to 20 carbon atoms, more preferably each Q is a
fluorinated aryl group, and most preferably each Q is a
pentafluoryl aryl group. Examples of suitable A.sup.d- also include
diboron compounds as disclosed in U.S. Pat. No. 5,447,895, which is
fully incorporated herein by reference.
Supports, Carriers and General Supporting Techniques
[0064] The Group 15 atom and metal catalyst compound, prepared in
accordance with the invention may be combined with a support
material or carrier, or with a supported activator. For example,
the catalyst compound is deposited on, contacted with, vaporized
with, bonded to, or incorporated within, adsorbed or absorbed in,
or on, a support or carrier.
[0065] The support material is any of the conventional support
materials. Preferably the supported material is a porous support
material, for example, talc, inorganic oxides and inorganic
chlorides. Other support materials include resinous support
materials such as polystyrene, functionalized or crosslinked
organic supports, such as polystyrene divinyl benzene polyolefins
or polymeric compounds, zeolites, clays, or any other organic or
inorganic support material and the like, or mixtures thereof
[0066] The preferred support materials are inorganic oxides that
include those Group 2, 3, 4, 5, 13 or 14 metal oxides. The
preferred supports include silica, fumed silica, alumina (WO
99/60033), silica-alumina and mixtures thereof. Other useful
supports include magnesia, titania, zirconia, magnesium chloride
(U.S. Pat. No. 5,965,477), montmorillonite (European Patent EP-B1 0
511 665), phyllosilicate, zeolites, talc, clays (U.S. Pat. No.
6,034,187) and the like. Also, combinations of these support
materials may be used, for example, silica-chromium,
silica-alumina, silica-titania and the like. Additional support
materials may include those porous acrylic polymers described in EP
0 767 184 B 1, which is incorporated herein by reference. Other
support materials include nanocomposites as described in PCT WO
99/47598, aerogels as described in WO 99/48605, spherulites as
described in U.S. Pat. No. 5,972,510 and polymeric beads as
described in WO 99/50311, which are all herein incorporated by
reference. A preferred support is fumed silica available under the
trade name Cabosil..TM.. TS-610, available from Cabot Corporation.
Fumed silica is typically a silica with particles 7 to 30
nanometers in size that has been treated with
dimethylsilyldichloride such that a majority of the surface
hydroxyl groups are capped.
[0067] It is preferred that the support material, most preferably
an inorganic oxide, has a surface area in the range of from about
10 to about 700 m.sup.2/g, pore volume in the range of from about
0.1 to about 4.0 cc/g and average particle size in the range of
from about 5 to about 500 microns. More preferably, the surface
area of the support material is in the range of from about 50 to
about 500 m.sup.2/g, pore volume of from about 0.5 to about 3.5
cc/g and average particle size of from about 10 to about 200
microns. Most preferably the surface area of the support material
is in the range is from about 100 to about 400 m.sup.2/g, pore
volume from about 0.8 to about 3.0 cc/g and average particle size
is from about 5 to about 100 microns. The average pore size of the
carrier of the invention typically has pore size in the range of
from 10 to 1000 .ANG., preferably 50 to about 500 .ANG., and most
preferably 75 to about 350 .ANG..
Polymerization Processes
[0068] The catalyst compounds described herein are applicable to
any polymerization process, for example, by suspension, solution,
slurry, gas phase process, or a combination thereof, using known
equipment and reaction conditions, and is not limited to any
specific type of polymerization system. Thus, the catalyst
compounds described herein may also have applicability to many
types of processes, including but not limited to, gas phase,
gas/solid phase, liquid/solid phase, gas/liquid phase, and
gas/liquid/solid phase reactor systems including polymerization
reactor systems; gas phase, gas/solid phase, liquid/solid phase,
gas/liquid phase, and gas/liquid/solid phase mass transfer systems;
gas phase, gas/solid phase, liquid/solid phase, gas/liquid phase,
and gas/liquid/solid phase mixing systems; gas phase, gas/solid
phase, liquid/solid phase, gas/liquid phase, and gas/liquid/solid
phase heating or cooling systems; gas/solid phase and
gas/solid/liquid phase drying systems; etc.
EXAMPLES
[0069] It is to be understood that while the invention has been
described in conjunction with the specific embodiments thereof, the
foregoing description is intended to illustrate and not limit the
scope of the invention. Other aspects, advantages and modifications
will be apparent to those skilled in the art to which the invention
pertains.
General Procedure for the Palladium-Catalyzed Coupling of
Diethylenetriamine and 2,3,4,5,6-Pentamethylbromobenzene (Examples
1 and Comparative Examples 1-25)
[0070] In a drybox, palladium precatalyst (0.01 mmol), ligand (0.01
mmol), 2,3,4,5,6-pentamethylbromobenzene (227.0 mg, 1.00 mmol),
diethylenetriamine (56.7 .mu.L, 0.52 mmol), sodium tert-butoxide
(120.1 mg, 1.25 mmol), dodecane (50.0 .mu.L, 0.020 mmol), and 1 mL
of solvent were added to a 4 mL scintillation vial equipped with a
magnetic stir bar and sealed with a cap containing a PTFE septum.
Reactions were placed into a temperature controlled aluminum
heating block and samples were taken at various time points and
analyzed by GC/MS. Conversions were determined relative to an
internal standard (dodecane).
Example 1
[0071] The palladium catalyzed coupling of 2 equivalents of
2,3,4,5,6-pentamethylbromobenzene (PMBB) and diethylenetriamine
(DETA) to selectively yield
N.sup.1-(2,3,4,5,6-pentamethylphenyl)-N.sup.2-(2-(2,3,4,5,6-pentamethylph-
enylamino)ethyl)ethane-1,2-diamine (reaction IV above) was
performed using a palladium complex with CyPF-t-Bu. The palladium
complex with CyPF-t-Bu was formed using a palladium acetate
(Pd(OAc).sub.2) as a catalyst precursor.
Comparative Examples 1-25
[0072] The reactive coupling of DETA and PMBB was performed using
comparative palladium catalysts as shown in Table 1, formed from
the listed palladium precursor and ligand. The abbreviated ligands
shown in Table 1 are detailed in the Table 1 Key.
[0073] For each of Example 1 and Comparative Examples 2-23, the
reaction was performed using approximately 1 mole percent catalyst,
2.5 equivalents of base (NaO.sup.tBu), dodecane as an internal
standard, in a solvent, where the reaction was performed at
100.degree. C. Reaction conditions for Comparative Example 1
included 1 mole percent palladium, 1 mole percent ligand, 1 mmol
PMBB, 0.5 mmol DETA, 1.25 mmol NaO.sup.tBu, and 1 mL solvent, where
the reaction was performed at 25.degree. C.
TABLE-US-00001 TABLE 1 Con- Time version Reaction Pd Precursor
Ligand Solvent (h) (%) Example 1 Pd(OAc).sub.2 CyPF-t- DME 0.25
99.6 Bu Comp. Ex. 1 (SiPr)Pd(allyl)Cl CyPF-t- DME 0.5 65.3 Bu Comp.
Ex. 2 (SiPr)Pd(allyl)Cl CyPF-t- DME 2.0 66.5 Bu Comp. Ex. 3
Pd.sub.2dba.sub.3 Binap Toluene 2 80.2 Comp. Ex. 4
Pd.sub.2dba.sub.3 Binap Toluene 3.5 93.2 Comp. Ex. 5
Pd.sub.2dba.sub.3 15-1048 Toluene 2 0.0 Comp. Ex. 6 Pd(OAc).sub.2
15-1048 Toluene 2 8.4 Comp. Ex. 7 Pd.sub.2dba.sub.3 15-1052 Toluene
2 6.3 Comp. Ex. 8 Pd(OAc).sub.2 15-1052 Toluene 2 7.1 Comp. Ex. 9
Pd.sub.2dba.sub.3 15-2975 Toluene 2 4.3 Comp. Ex. 10 Pd(OAc).sub.2
15-2975 Toluene 2 11.1 Comp. Ex. 11 Pd.sub.2dba.sub.3 15-1145
Toluene 0.5 61.2 Comp. Ex. 12 Pd.sub.2dba.sub.3 15-1145 Toluene 2
68.3 Comp. Ex. 13 Pd(OAc).sub.2 15-1145 Toluene 2 34.3 Comp. Ex. 14
Pd.sub.2dba.sub.3 15-1149 Toluene 2 6.3 Comp. Ex. 15 Pd(OAc).sub.2
15-1149 Toluene 2 8.5 Comp. Ex. 16 Pd.sub.2dba.sub.3 15-2980
Toluene 2 4.3 Comp. Ex. 17 Pd(OAc).sub.2 15-2980 Toluene 2 12.0
Comp. Ex. 18 Pd.sub.2dba.sub.3 15-0380 Toluene 2 0.9 Comp. Ex. 19
Pd(OAc).sub.2 15-0380 Toluene 2 4.7 Comp. Ex. 20 Pd.sub.2dba.sub.3
15-1242 Toluene 2 26.3 Comp. Ex. 21 Pd(OAc).sub.2 15-1242 Toluene 2
6.1 Comp. Ex. 22 Pd.sub.2dba.sub.3 26-0275 Toluene 2 7.6 Comp. Ex.
23 Pd(OAc).sub.2 26-0275 Toluene 2 11.1 Comp. Ex. 24 46-0272 --
Toluene 2 25.8 Comp. Ex. 25 46-0025 -- Toluene 2 5.2
TABLE-US-00002 TABLE 1 Key: ##STR00011## ##STR00012## ##STR00013##
##STR00014## ##STR00015## ##STR00016## ##STR00017## ##STR00018##
##STR00019## ##STR00020##
[0074] As shown by the experimental results, the catalyst system of
Pd(OAc).sub.2/CyPF-t-Bu (Example 1) exhibits increased rates in
comparison to the catalyst systems of U.S. Pat. No. 6,518,444
(Table 1, entries 1 and 2) and outperforms all other catalyst
systems surveyed while maintaining excellent selectivity (>98%)
for the desired product. The benchmark catalyst system composed of
Pd.sub.2dba.sub.3 and rac-Binap performed as expected; after 3.5
hours the reaction yielded the desired product in 93.2% (Table 1,
Comparative Examples 3 and 4). Catalyst systems based on bulky
monodendate phosphines (Comparative Examples 5-10 and 14-17) and
wide bite-angle bidendate phosphines (Comparative Examples 18-23)
with either Pd.sub.2dba.sub.3 or Pd(OAc).sub.2 proved to be
inefficient, yielding less than 26.3% of the desired product after
2 hours at 100.degree. C. Cyclometallated palladium complexes
(entries 25 and 26) also proved unproductive. Modest yields were
achieved with Comparative Example 11 and Comparative Example 1,
although extended reaction times proved, for both catalysts, that
catalyst decomposition limited conversion. The catalyst system
according to embodiments disclosed herein, CyPF-t-Bu and
Pd(OAc).sub.2 demonstrated the highest activity of any catalyst
sampled, and the catalyst afforded the desired product in
quantitative yield in only 15 minutes (Example 1).
General Procedure for the Effect of Catalyst Concentration on the
Palladium-Catalyzed Coupling of Diethylenetriamine and
2,3,4,5,6-Pentamethvlbromobenzene (Examples 2-6 and Comparative
Example 26)
[0075] In a drybox, 2,3,4,5,6-pentamethylbromobenzene (227.0 mg,
1.00 mmol), diethylenetriamine (56.7 .mu.L, 0.52 mmol), sodium
tert-butoxide (120.1 mg, 1.25 mmol), dodecane (50.0 .mu.L, 0.020
mmol), and 1 mL of solvent were added to a 4 mL scintillation vial
equipped with a magnetic stirbar. An aliquot of a freshly prepared
10.0 mM solution of Pd(OAc).sub.2/CyPF-t-Bu was added and the
reaction was sealed with a cap containing a PTFE septum. Reactions
were placed into a temperature controlled aluminum heating block
and samples were taken a various time points and analyzed by GC/MS.
Conversions were determined relative to an internal standard
(dodecane).
Examples 2-6
[0076] The effect of reducing the catalyst loading was
investigated. Reaction profiles were monitored by GC while varying
catalyst concentrations between 0.025 and 1.0 mol % at similar
conditions as given for Example 1. Catalyst concentrations for each
Example are given in Table 2.
TABLE-US-00003 TABLE 2 Reaction Mol % Pd(OAc).sub.2/CyPF-t-Bu
Example 1 1.0 Example 2 0.5 Example 3 0.1 Example 4 0.075 Example 5
0.05 Example 6 0.025
Comparative Example 26
[0077] The reduced catalyst loading of Examples 1-6 were compared
to a reaction performed with 1.0 mol % Pd.sub.2(dba).sub.3/2.0 mol
% rac-Binap, also performed at similar conditions as given for
Comparative Example 3.
[0078] Samples were taken periodically during the duration of the
reaction and analyzed for conversion of the reactants to the N-aryl
amine. Conversion versus time results for the reactions is shown in
FIG. 1. The reaction analyses clearly indicate that the
Pd(OAc).sub.2/CyPF-t-Bu, even at the reduced loading, had better
activity than the catalyst of Comparative Example 26.
[0079] Reactions conducted with 1.0 or 0.5 mol % catalyst (Examples
1 and 2) were indistinguishable, reaching complete conversion by
the first data point. Subsequent reactions with reduced catalyst
loadings were distinguishable; reactions conducted with 0.1 mol %
(Example 3), 0.075 mol % (Example 4), and 0.05 mol % (Example 5)
reached complete conversion at 60 minutes, 180 minutes, and
.gtoreq.180 minutes, respectively. Interestingly, reducing the
catalyst concentration to 0.025 mol % resulted in failure to
achieve complete conversion even with prolonged reaction times,
presumably due to catalyst decomposition.
Examples 7-11
[0080] Coupling reactions using catalyst compositions according to
embodiments disclosed herein was also conducted at a larger scale,
at approximately 250 time the scale of Example 1. The only notable
change in procedure as compared to Example 1, to facilitate an
easier workup, was the devolatilization of the reaction solvent
prior to partitioning between an aqueous/organic system. In
addition to the amination of PMBB with diethylenetriamene, the
arylation of 1,5-diaminopentane and 2,2'-oxydimethylamine were also
investigated. Experimental procedures are given below for each
Example, followed by a summary of results in Table 3.
Large Scale Preparation of
N1-(2,3,4,5,6-pentamethylphenyl)-N2-(2-(2,3,4,5,6-pentamethylphenylamino)-
ethyl)ethane-1,2-diamine (Example 7).
[0081] In a drybox, 2,3,4,5,6-pentamethylbromobenzene (57.50 g,
253.2 mmol), sodium tert-butoxide (30.41 g, 316.4 mmol), 250 mL of
anhydrous DME, and diethylenetriamine (13.81 mL, 127.8 mmol) were
combined in an oven-dried 500 mL round bottom flask equipped with a
magnetic stirbar. Pd(OAc)2 (14.2 mg, 0.0632 mmol), CyPF-t-Bu (35.1
mg, 0.0633 mmol), and DME (dimethyl ether, 2 mL) were combined in a
separate 4 mL scintillation vial and stirred until homogenous
before addition to the former solution. A reflux condenser was
fitted to the reaction which was subsequently heated to 100.degree.
C. overnight (14 h). After cooling the reaction to room temperature
complete conversion was confirmed by GC/MS. All volatiles were
removed by rotary evaporation and the residue was partitioned
between 400 mL H2O/CH2Cl2 (1:1). The organic fraction was separated
and the aqueous phase washed with two 50 mL portions of CH2Cl2. The
organic fractions were combined and dried over MgSO4. The
suspension was filtered and all volatile materials were removed by
rotary evaporation to afford
N1-(2,3,4,5,6-pentamethylphenyl)-N2-(2-(2,3,4,5,6-pentamethylphenylamino)-
ethyl)ethane-1,2-diamine (49.79 g, 99.4%) as a light tan solid.
[0082] .sup.1H NMR spectra were obtained at 400 MHz and recorded
relative to residual protio solvent. .sup.13C NMR spectra were
obtained at 101 MHz and recorded relative to the residual solvent
resonance. The spectra recorded are as follows: .sup.1H NMR (CDCl3,
400 MHz, 22 .degree. C.): .epsilon. 2.34 (s, 6H), 2.36 (s, 12H),
2.42 (s, 12H), 3.02-3.05 (m, 4H), 3.09-3.12 (m, 4H). .sup.13C NMR
(CDCl3, 101 MHz, 22.degree. C.): .epsilon. 14.8, 16.4, 16.7, 49.4,
50.0, 126.8, 129.5, 132.8, 143.5.
N1 ,N5-b is (2,3,4,5,6-pentamethylphenyl)pentane-1,5-diamine
(Example 8)
[0083] In a drybox, 2,3,4,5,6-pentamethylbromobenzene (750.0 mg,
3.30 mmol), 1,5-pentanediamine (195.2 .mu.L, 1.67 mmol), sodium
tertbutoxide (396.6 mg, 4.13 mmol), 3.0 mL of dimethyoxyethane, and
10.0 mM Pd(OAc)2/CyPF-t-Bu (82.5 .mu.L, 8.25.times.10-4 mmol) were
added to a 20 mL scintillation vial equipped with a magnetic
stirbar and sealed with a cap containing a PTFE septum. The
reaction was placed into a temperature controlled aluminum heating
block and stirred at 100.degree. C. for 6 h. After cooling to room
temperature, the reaction mixture was partitioned between 100 mL
H2O/Diethyle ether (Et2O) (1:1), the organic phase separated and
dried over MgSO4, followed by the removal of all volatiles to
afford 619 mg (95.0%) of the title compound.
[0084] .sup.1H NMR spectra were obtained at 400 MHz and recorded
relative to residual protio solvent. .sup.13C NMR spectra were
obtained at 101 MHz and recorded relative to the residual solvent
resonance. The spectra recorded are as follows: 1H NMR (CDCl3, 400
MHz, 22.degree. C.): .epsilon. 1.50-1.71(m, 6H), 2.21 (s, 6H), 2.22
(s, 12H), 2.25 (s, 12H), 2.84 (t, J=7.2 Hz, 4H), 2.88 (br s, 2H).
.sup.13C NMR (CDCl3, 101 MHz, 22.degree. C.): 6 14.8, 16.5, 16.9,
25.0, 30.9, 49.9, 126.8, 129.6, 132.9, 143.7.
N,N'-(2,2'-oxybis(ethane-2,1-diyl))bis(2,3,4,5,6-pentamethylaniline)
(Example 9)
[0085] In a drybox, 2,3,4,5,6-pentamethylbromobenzene (750.0 mg,
3.30 mmol), 2,2'-oxydiethylamine dihydrochloride (295.3 mg, 1.67
mmol), sodium tert-butoxide (714.0 mg, 7.43 mmol), 3.0 mL of
dimethyoxyethane, and 10.0 mM Pd(OAc)2/CyPF-t-Bu (82.5 .mu.L,
8.25.times.10-4 mmol) were added to a 20 mL scintillation vial
equipped with a magnetic stirbar and sealed with a cap containing a
PTFE septum. The reaction was placed into a temperature controlled
aluminum heating block and stirred at 100.degree. C. for 6 h. After
cooling to room temperature, the reaction mixture was partitioned
between 100 mL H2O/Et2O (1:1), the organic phase separated and
dried over MgSO4, followed by the removal of all volatiles to
afford 611 mg (93.3%) of the title compound.
[0086] .sup.1H NMR spectra were obtained at 400 MHz and recorded
relative to residual protio solvent. .sup.13C NMR spectra were
obtained at 101 MHz and recorded relative to the residual solvent
resonance. The spectra recorded are as follows:.sup.1H NMR (CDCl3,
400 MHz, 22.degree. C.): .epsilon. 2.22 (s, 6H), 2.23 (s, 12H),
2.29 (s, 12H), 3.07 (t, J=5.0 Hz, 4H), 3.55 (br s, 2H), 3.67 (t,
J=5.0 Hz, 4H). .sup.13C NMR (CDCl3, 101 MHz, 22.degree. C.): 6
14.7,16.6, 16.8, 49.3, 70.6, 127.0, 129.7, 133.0, 143.1.
N1,N5 -dimesitylpentane-1,5-diamine (Example 10)
[0087] In a drybox, 2,4,6-trimethylbromobenzene (750.0 .mu.L, 4.90
mmol), 1,5-pentanediamine (286.8 .mu.L, 2.45 mmol), sodium
tert-butoxide (588.7 mg, 6.13 mmol), 4.0 mL of dimethyoxyethane,
and 10.0 mM Pd(OAc)2/CyPF-t-Bu (123 .mu.L, 1.23.times.10-3 mmol)
were added to a 20 mL scintillation vial equipped with a magnetic
stirbar and sealed with a cap containing a PTFE septum. The
reaction was placed into a temperature controlled aluminum heating
block and stirred at 100.degree. C. for 6 h. After cooling to room
temperature, the reaction mixture was partitioned between 100 mL
H2O/Et2O (1:1), the organic phase separated and dried over MgSO4,
followed by the removal of all volatiles to afford 821 mg (99.0%)
of the title compound.
[0088] .sup.1H NMR spectra were obtained at 400 MHz and recorded
relative to residual protio solvent. .sup.13C NMR spectra were
obtained at 101 MHz and recorded relative to the residual solvent
resonance. The spectra recorded are as follows:.sup.1H NMR (CDCl3,
400 MHz, 22.degree. C.): .epsilon. 1.45-1.54 (m, 2H), 1.59-1.67 (m,
4H), 2.24 (s, 6H), 2.26 (s, 12H), 2.87 (br s, 2H), 2.95 (t, J=7.2
Hz, 4H), 6.83 (s, 4H). .sup.13C NMR (CDCl3, 101 MHz, 22.degree.
C.): .epsilon. 18.3, 20.5, 24.8, 31.0, 48.8, 129.4, 129.5, 131.1,
143.7.
N,N'-(2,2'-oxybis(ethane-2,1-diyl))bis(2,4,6-trimethylaniline)
(Example 11)
[0089] In a drybox, 2,4,6-trimethylbromobenzene (500.0 .mu.L, 3.27
mmol), 2,2'-oxydiethylamine dihydrochloride (289.3 mg, 1.63 mmol),
sodium tert-butoxide (706.5 mg, 7.35 mmol), 4.0 mL of
dimethyoxyethane, and 10.0 mM Pd(OAc)2/CyPF-t-Bu (81.8 .mu.L,
8.18.times.10-4 mmol) were added to a 20 mL scintillation vial
equipped with a magnetic stirbar and sealed with a cap containing a
PTFE septum. The reaction was placed into a temperature controlled
aluminum heating block and stirred at 100.degree. C. for 6 h. After
cooling to room temperature, the reaction mixture was partitioned
between 100 mL H2O/Et2O (1:1), the organic phase separated and
dried over MgSO4, followed by the removal of all volatiles to
afford 505 mg (91.0%) of the title compound.
[0090] .sup.1H NMR spectra were obtained at 400 MHz and recorded
relative to residual protio solvent. .sup.13C NMR spectra were
obtained at 101 MHz and recorded relative to the residual solvent
resonance. The spectra recorded are as follows:.sup.1H NMR (CDCl3,
400 MHz, 22.degree. C.): .epsilon. 2.24 (s, 6H), 2.28 (s, 12H),
3.15 (t, J=5.0 Hz, 4H), 3.49 (br s), 3.61 (t, J=5.0 Hz, 4H), 6.84
(s, 4H). .sup.13C NMR (CDCl3, 101 MHz, 22.degree. C.): 8 18.2,
20.5, 48.2, 70.4, 129.4, 129.8, 131.3, 143.1.
TABLE-US-00004 TABLE 3 Exam- Yield ple Aryl Bromide Diamine % 7
##STR00021## ##STR00022## 99.4 8 ##STR00023## ##STR00024## 95.0 9
##STR00025## ##STR00026## 93.3 10 ##STR00027## ##STR00028## 99.0 11
##STR00029## ##STR00030## 91.0
[0091] As shown by the above results, the larger scale amination of
PMBB with diethylenetriamine was successfully performed at more
than 250 time the scale of Example 1, without sacrificing yield or
selectivity. Additionally, the arylation of both diamines
(1,5-diaminopentane and 2,2'-oxydiethylamine) with either PMBB or
2,4,6-trimethylbromobenzene proceeded cleanly, affording the
desired arylated diamines in near quantitative yields.
[0092] As described above, Group 8 transition metal catalysts
complexes with CyPF-t-Bu may be used to effectively catalyze
reactions between nitrogen-containing compounds and arylating
agents to form N-aryl amines, which may be used to form
polymerization catalysts. In particular, it has been found that
palladium acetate/CyPF-t-Bu complexes may achieve greater than 99%
conversion at selectivities of at least 98%, where the high
conversions may be achieved at reaction times significantly lower
than that required by comparative palladium catalysts to reach 80
or 90% conversion.
[0093] The phrases, unless otherwise specified, "consists
essentially of" and "consisting essentially of" do not exclude the
presence of other steps, elements, or materials, whether or not,
specifically mentioned in this specification, so long as such
steps, elements, or materials, do not affect the basic and novel
characteristics of the invention, additionally, they do not exclude
impurities and variances normally associated with the elements and
materials used.
[0094] Only certain ranges are explicitly disclosed herein.
However, ranges from any lower limit may be combined with any upper
limit to recite a range not explicitly recited, as well as, ranges
from any lower limit may be combined with any other lower limit to
recite a range not explicitly recited, in the same way, ranges from
any upper limit may be combined with any other upper limit to
recite a range not explicitly recited. Additionally, within a range
includes every point or individual value between its end points
even though not explicitly recited. Thus, every point or individual
value may serve as its own lower or upper limit combined with any
other point or individual value or any other lower or upper limit,
to recite a range not explicitly recited.
[0095] All documents cited herein are fully incorporated by
reference for all jurisdictions in which such incorporation is
permitted and to the extent such disclosure is consistent with the
description of the present invention.
[0096] While the invention has been described with respect to a
number of embodiments and examples, those skilled in the art,
having benefit of this disclosure, will appreciate that other
embodiments can be devised which do not depart from the scope and
spirit of the invention as disclosed herein.
* * * * *