Organic compounds -- part of the class 532-570 series – Organic compounds – Phosphorus containing
Reexamination Certificate
2001-04-09
2003-10-07
Riley, Jezia (Department: 1637)
Organic compounds -- part of the class 532-570 series
Organic compounds
Phosphorus containing
C568S017000, C436S501000, C436S518000, C530S333000, C530S335000
Reexamination Certificate
active
06630604
ABSTRACT:
FIELD OF INVENTION
This invention relates to the preparation of novel polymer-supported phosphine and phosphine oxide compounds and the corresponding free compounds after cleavage from support. These compounds are useful as ligands in the preparation of metal-containing catalysts.
BACKGROUND
As is generally known in prior art, chelating phosphine compounds when bound to metal atoms are useful as catalysts. To facilitate separation of the catalysts from a chemical process, phosphorus ligands have been attached to solid supports such as polymers (“Supported Metal Complexes”, D. Reidel Publishing, 1985; Acta. Polymer. 1996, 47, 1
; “Chem. Met
.-
Carbon Bond
”, Hartley, F. R (Ed), 1987, vol. 4, pp. 1163-1225; Neckers,
J. Macromol. Sci., Chem
. 1987, A24, 431-48). Interest in using the combinatorial “split and mix synthesis” approach to generate polymer-bound ligands which could be tested as catalysts has brought to fore the importance of new chemistry with which to attach phosphine ligands to polymer supports (Balkenhohl et al.,
Angew. Chem., Int. Ed. Engl
. 1996, 35, 2288-2337; Gilbertson et al.,
J. Organometallics
1996, 15, 4678-4680; Gilbertson et al.,
J. Am. Chem. Soc
. 1994, 116, 4481-4482).
Novel processes have been discovered to prepare new compositions of matter that contain chelating phosphine compounds, including compounds of asymmetric diphosphines. Phosphine compounds have been shown to be useful when combined with transition metals as catalysts for chemical processes. The processes can also be utilized in a combinatorial scheme to produce libraries of phosphine compounds.
Addition of aldehyde in salicylaldehydes to acetylenes is known, but is unknown for addition to alkenes. (Kokai Tokkyo Koho JP 7853632; JP 76128205 Kokubo et al.,
J. Org. Chem
. 1997, 62, 4564-4565.) The new phosphorus compounds have been shown to be useful as ligands in catalysts for the decarbonylation of the salicylaldehyde and insertion of the alkene, followed by ring closure forming a coumarin.
SUMMARY OF THE INVENTION
This invention is directed to compositions and processes to prepare polymer supported phosphine and phosphine oxide compounds and the corresponding free compounds after their cleavage from the polymer support.
More specifically, the invention is directed to a process to prepare a supported phosphine compound selected from the group consisting of Formulae 1, 2, 3, 4, 5, 6, and 7
wherein:
SS is a solid support; A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R
1
, R
2
, and R
3
are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometallic, Cl, Br, I, SQ
1
, OQ
2
, PQ
3
Q
4
, and NQ
5
Q
6
, where Q
1
, Q
2
, Q
3
, Q
4
, Q
5
, and Q
6
are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R
2
and R
3
together, R
1
and R
3
together, or R
1
and R
2
together can optionally form a ring, the process comprising the steps of:
a) contacting (i) a phosphine selected from the group consisting of XPR
1
R
2
, XR
3
P—A—PR
1
R
2
, HP(═O)R
1
R
2
, HP(═O)R
3
—A—PR
1
R
2
, and HP(═O)R
3
—A—P(═O)R
1
R
2
wherein X is a halogen, with (ii) the solid support, resulting in at least one P in the phosphine attached indirectly or directly to the solid support via one or more covalent bonds, and
b) optionally replacing one or more substituent of the group R
1
, R
2
, or R
3
with any other substituent of the group R
1
, R
2
, or R
3
.
In all process and compositions embodiments of the invention, the preferred SS is selected from the group consisting of polyolefins, polyacrylates, polymethacrylates, and copolymers thereof.
The process is useful in producing the preferred supported phosphine compounds selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A.
wherein:
Z is a divalent attaching group covalently attached to at least one P in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, —O—, —S—, and —NR
4
—, where R
4
is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and
L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.
More particularly, this process to prepare supported phosphine compounds uses the supported phosphine compound of Formula 1A, where the process comprises the steps of:
a) contacting (i) at least 2 molar equivalents of a phosphine of the Formula XR
3
P—A—PR
1
R
2
wherein X is a halogen, with (ii) no more than one molar equivalent of Z, resulting in one P in the phosphine being covalently bonded to the Z, and
b) optionally replacing one or more substitutent of the group R
1
, R
2
, and R
3
with any one or more of R
1
, R
2
, and R
3
. In this process the SS is more preferably polystyrene; L is —CH
2
—; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, —(NR
4
)—, and —O—; R
4
is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; R
1
, R
2
, and R
3
are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ
1
, OQ
2
, and PQ
3
Q
4
, where Q
1
, Q
2
, Q
3
, and Q
4
are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R
1
and R
2
together with the P form a phosphole, aryl, or alkyl ring.
Alternatively, the process may use a supported phosphine compound of Formula 2A, with the process comprising the steps of:
a) contacting (i) a phosphine of the Formula PR
1
R
2
X wherein X is a halogen, with (ii) the solid support, resulting in one P in the phosphine being covalently bonded to Z, and
b) optionally replacing one or both of R
1
and R
2
with any other R
1
or R
2
. In this process the SS is more preferably polystyrene; is —CH
2
—; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, —(NR
4
)—, and —O—; R
4
is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R
1
and R
2
are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ
1
, OQ
2
, and PQ
3
Q
4
, where Q
1
, Q
2
, Q
3
, and Q
4
are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R
1
and R
2
together with the P form a phosphole, aromatic or alkyl ring.
Alternatively, this process may use the supported phosphine compound of Formula 3A, with the process comprising the steps of:
a) contacting (i) no more than one molar equivalent of a phosphine of the Formula XR
3
P—A—PR
1
R
2
wherein X is a halogen, with (ii) at least two molar equivalents of Z, resulting in both of the P in the phosphine being covalently bonded to the Z; and
b) optionally replacing one or more of R
1
and R
2
with any one or more of R
1
and R
2
. In this process the SS is more preferably polystyrene; L is —CH
2
—; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, —(NR
4
)—, and —O—; R
4
is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; R
1
and R
2
are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ
1
, OQ
2
, and PQ
3
Q
4
, where Q
1
, Q
2
, Q
3
, and Q
4
are selecte
Belopolsky Inna Y.
E. I. du Pont de Nemours and Company
Riley Jezia
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