Unlock instant, AI-driven research and patent intelligence for your innovation.
Phosphino-aminophosphines
What is Al technical title?
Al technical title is built by PatSnap Al team. It summarizes the technical point description of the patent document.
A residue, methyl technology, applied in the field of bis-phosphine compounds, can solve the problems of no metallocene moiety, unreported chirality, non-racemic bis-phosphine ligands, etc.
Inactive Publication Date: 2005-05-04
EASTMAN CHEM CO
View PDF0 Cites 5 Cited by
Summary
Abstract
Description
Claims
Application Information
AI Technical Summary
This helps you quickly interpret patents by identifying the three key elements:
Problems solved by technology
Method used
Benefits of technology
Problems solved by technology
Fiorini, M. and Giongo, G.M.J.Mol.Cat.1979, 5,303-310 and Pracejus, G.; Pracejus, H.Tetrahedron Lett.1977, 3497-3500, reported that bis-aminophosphine-based asymmetric ligands can Provides moderately effective asymmetric hydrogenation (<90% enantiomeric excess-ee), but in all cases these ligands do not have a metallocenemoiety or a mixture of carbon and nitrogen-bonded phosphines
In fact, chiral, non-racemic, bis-phosphine ligands in which one phosphine is bonded to three carbon atoms and the other to two carbon atoms and one nitrogen atom have not been reported.
Method used
the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more
Image
Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
Click on the blue label to locate the original text in one second.
Reading with bidirectional positioning of images and text.
[0045] (R)-N, N-dimethyl-1-[(S)-2-(diphenylphosphino) ferrocenyl] ethylamine (R, S-3a, R=R 8 =R 9 = methyl, R 3 =Phenyl-Ph,R 4 =R 5 =H, M=Fe)) (10.0 g; 22.7 mmol) and acetic anhydride (14.25 mL; 150 mmol; 6.7 equiv) were mixed in a 250-mL flask. The flask was evacuated and filled ten times with nitrogen, then heated to 100°C for 2 hours, at which time thin layerchromatography (tlc) analysis showed no 3a was present. Residual acetic anhydride was evaporated under reduced pressure to give a solid material comprising acetate R,S-4a. A portion (1.0 g) of the acetate R, S-4a was removed, the residue was dissolved in isopropanol (200 mL) and washed with concentrated ammonia (28% NH 3 ; 24.3mL; 360mmol; 17.5 equivalents) treatment. The reaction mixture was heated to 50 °C overnight to completely consume 4 (according to TLC analysis). The mixture was concentrated to a small volume un...
Embodiment 2
[0052] (S)-N-methyl-1-[(R)-2-(diphenylphosphino)-ferrocenyl]ethylamine (S, R-8b)(R 1 = Preparation of Me)
[0053] (S)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (S,R-6a) (5.0 g; 11.3 mmol) Mix with acetic anhydride (7.1 mL; 75.2 mmol; 6.7 equiv) in a 100-mL flask. The flask was evacuated and filled ten times with nitrogen, then heated to 100°C for 2 hours, at which time thin layerchromatography analysis showed no 6a was present. Residual acetic anhydride was evaporated under reduced pressure to give a solid material comprising acetate S, R-7a. This material was dissolved in isopropanol (110 mL) and treated with 40% aqueous methylamine (14..6 mL; 170 mmol; 15 equiv). The reaction mixture was heated to 50 °C for 48 hours to completely consume 7a (according to TLC analysis). The mixture was concentrated to a small volume under reduced pressure. The residue was dissolved in 1:1 ethyl acetate:heptane and extracted with 10% aqueous citric acid (4 x 10 mL)....
Embodiment 3
[0060] Preparation of (R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyl acetate (R, S-4a)
[0061] (R)-N,N-Dimethyl-1-[(S)-2-(diphenylphosphino)ferrocenyl]-ethylamine (R,S-3a) (10.4g; 24.0mmol ) was mixed with acetic anhydride (15 mL; 136 mmol; 5.7 equiv) in a 100-mL flask. The flask was evacuated and filled ten times with nitrogen, then heated to 100°C for 2 hours, at which time thin layerchromatography analysis showed no 3a was present. Residual acetic anhydride was evaporated under reduced pressure to give acetate R,S-4a. This material was recrystallized from ethyl acetate-heptane mixtures.
the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More
PUM
Property
Measurement
Unit
thickness
aaaaa
aaaaa
Login to View More
Abstract
Disclosed are substantially enantiomerically pure bis-phosphine compounds comprising a substantially enantiomerically pure chiral backbone linking two phosphine residues wherein one of the phosphine residues has three phosphorus-carbon bonds and the other phosphine residue has two phosphorus-carbon bonds and one phosphorus-nitrogen bond wherein the nitrogen is part of the chiral backbone. The compounds, which have exhibited surprising air stability, are useful as ligands for metal catalysts for asymmetric reactions and have demonstrated excellent results, in particular as rhodium complexes for asymmetric hydrogenation of enamide, itaconate, and alpha -ketoester compounds. Also disclosed are novel processes for the preparation of the bis-phosphine compounds and novel intermediate compounds useful in the preparation of the bis-phosphine compounds.
Description
[0001] Cross References to Related Applications [0002] This application claims the benefit of US Provisional Application Serial Nos. 60 / 236,564 (filed September 29, 2000) and 60 / 264,411 (filed January 26, 2001). technical field [0003] The present invention relates to novel, substantially enantiomerically pure, bis-phosphine compounds characterized by having both carbon-bonded and nitrogen-bonded phosphines linked by divalent chiral groups. The compounds are useful as ligands for metal catalysts for asymmetric reactions and have surprising stability and excellent effects, especially as ligands for rhodium complexes for asymmetric hydrogenations. The present invention also relates to novel processes and intermediate compounds useful for the preparation of said bis-phosphine compounds, to compounds comprising one or more bis-phosphine compounds in complex with one or more Group VIII metals Association, and its use for asymmetric hydrogenation. Background technique [0004...
Claims
the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More
Application Information
Patent Timeline
Application Date:The date an application was filed.
Publication Date:The date a patent or application was officially published.
First Publication Date:The earliest publication date of a patent with the same application number.
Issue Date:Publication date of the patent grant document.
PCT Entry Date:The Entry date of PCT National Phase.
Estimated Expiry Date:The statutory expiry date of a patent right according to the Patent Law, and it is the longest term of protection that the patent right can achieve without the termination of the patent right due to other reasons(Term extension factor has been taken into account ).
Invalid Date:Actual expiry date is based on effective date or publication date of legal transaction data of invalid patent.
Login to View More