Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2001-04-11
2004-04-06
Davis, Zinna Northington (Department: 1625)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
active
06716984
ABSTRACT:
FIELD OF INVENTION
The invention relates to the combinatorial approaches to the preparation of novel polymer-supported heteroatom bidentate (PN, PO, PS) ligand libraries and the corresponding free compounds after cleavage from the supports. These compounds are useful as novel ligands in the preparation of metal-containing catalysts.
BACKGROUND
Chelating phosphine compounds 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. 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.
Novel processes have been discovered to prepare new compositions of matter that contain chelating phosphine compounds, including compounds of asymmetric and unsymmetric diphosphines using solid supports. 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. These processes and the compounds prepared are described in U.S. patent application Ser. No. 09/415,347, filed Oct. 8, 1999.
Rapid, clean, high-yielding processes are needed, however, in which a variety of phosphine ligands are prepared. Especially needed are processes to prepare heteroatom bidentate phosphine ligands which are difficult to prepare using traditional methods as the intermediates are generally unstable. Processes are also needed that prepare these ligands in a library format and use chiral substituents.
SUMMARY OF INVENTION
The invention is directed towards a process to prepare a supported phosphine compound of Formula 1:
wherein SS is a solid support; R
1
is selected from the group consisting of halogen, hydrocarbyl, substituted hydrocarbyl, heterocyclic and substituted heterocyclic; and R
2
is selected from the group consisting of halogen, cyclic hydrocarbyl, substituted cyclic hydrocarbyl, heterocyclic and substituted heterocyclic. The process comprises the steps of: a) contacting a phosphine of the formula XPR
1
R
2
, wherein X is a halogen, with the solid support, resulting in the P in the phosphine attached indirectly or directly to the solid support via covalent bonds, and b) optionally replacing one or more of R
1
or R
2
with any other R
1
or R
2
respectively.
Preferably, SS is selected from the group consisting of polyolefins, polyacrylates, polymethacrylates, and copolymers thereof.
Also preferably, the supported phosphine compound is of Formula 1A:
wherein Z is a divalent or trivalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, —O—, —S—, and —NQ—, where Q 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. Most preferably, SS is polystyrene; L is —CH
2
—; Z is —(NQ)—; Q is selected from the group consisting of n-propyl, and t-butyl; R
1
is selected from the group consisting of bromo, chloro, phenyl, methyl, i-propyl, mesityl, cyclohexyl, 3-methoxyphenyl, and 2-thienyl, —CH
2
CH(C
2
H
5
)CH
2
O(CH
2
)
3
CH
3
, and —CH
2
CH(C
2
H
5
)CH
2
OCH
2
C
6
H
5
; and R
2
is selected from the group consisting 2-furanyl, 2-(5-methylfuranyl), 2-thienyl, 2,4-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-N,N-dimethyl-5-toluidinyl, 4-pyrrolidino-3-pyridinyl, 2,5-dimethyl-1-N(4′-methylphenyl)pyrrolidinyl, p-[(2,5-dimethyl)-1-pyrrolidinyl]phenyl, and 2,5-dimethoxylphenyl.
The invention is also directed towards supported phosphine compounds of Formula 1:
wherein SS is a solid support; R
1
is selected from the group consisting of halogen, hydrocarbyl, substituted hydrocarbyl, heterocyclic and substituted heterocyclic; and R
2
is selected from the group consisting of cyclic hydrocarbyl, substituted cyclic hydrocarbyl, heterocyclic and substituted heterocyclic.
Preferably, SS is selected from the group consisting of polyolefins, polyacrylates, polymethacrylates, and copolymers thereof.
Also preferably, the supported phosphine compound is of Formula 1A:
wherein Z is a divalent or trivalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, —O—, —S—, and —NQ—, where Q 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. Most preferably, SS is polystyrene; L is —CH
2
—; Z is —(NQ)—; Q is selected from the group consisting of n-propyl, and t-butyl; R
1
is selected from the group consisting of bromo, chloro, phenyl, methyl, i-propyl, mesityl, cyclohexyl, 3-methoxyphenyl, and 2-thienyl, —CH
2
CH(C
2
H
5
)CH
2
O(CH
2
)
3
CH
3
, and —CH
2
CH(C
2
H
5
)CH
2
OCH
2
C
6
H
5
; and R
2
is selected from the group consisting 2-furanyl, 2-(5-methylfuranyl), 2-thienyl, 2,4-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-N,N-dimethyl-5-toluidinyl, 4-pyrrolidino-3-pyridinyl, 2,5-dimethyl-1-N(4′-methylphenyl)pyrrolidinyl, 2,5-dimethyl-1-N-phenylpyrrolidinyl, and 2,5-dimethoxylphenyl.
DETAILED DESCRIPTION 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 towards a process to prepare a supported phosphine compound of Formula 1:
wherein SS is a solid support; R
1
is selected from the group consisting of halogen, hydrocarbyl, substituted hydrocarbyl, heterocyclic and substituted heterocyclic; and R
2
is selected from the group consisting of halogen, cyclic hydrocarbyl, substituted cyclic hydrocarbyl, heterocyclic and substituted heterocyclic. The process comprises the steps of: a) contacting a phosphine of the formula XPR
1
R
2
, wherein X is a halogen, with the solid support, resulting in the P in the phosphine attached indirectly or directly to the solid support via a covalent bonds, and b) optionally replacing one or more of R
1
or R
2
with any other R
1
or R
2
.
Preferably, SS is selected from the group consisting of polyolefins, polyacrylates, polymethacrylates, and copolymers thereof.
Also preferably, the supported phosphine compound is of Formula 1A:
wherein Z is a divalent or trivalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, —O—, —S—, and —NQ—, where Q 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. Most preferably, SS is polystyrene; L is —CH
2
—; Z is —(NQ)—; Q is selected from the group consisting of n-propyl, and t-butyl; R
1
is selected from the group consisting of bromo, chloro, phenyl, methyl, i-propyl, mesityl, cyclohexyl, 3-methoxyphenyl, and 2-thienyl, —CH
2
CH(C
2
H
5
)CH
2
O(CH
2
)
3
CH
3
, and —CH
2
CH(C
2
H
5
)CH
2
OCH
2
C
6
H
5
; and R
2
is selected from the group consisting 2-furanyl, 2-(5-methylfuranyl), 2-thienyl, 2,4-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-N,N-dimethyl-5-toluidinyl, 4-pyrrolidino-3-pyridinyl, 2,5-dimethyl-1-N(4′-methylphenyl)pyrrolidinyl, p-[(2,5-dimethyl)-1-pyrrolidinyl]phenyl, and 2,5-dimethoxylphenyl.
The in
Belopolsky Inna Y.
Davis Zinna Northington
E. I. du Pont de Nemours and Company
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