Method of compounding eight-hydrogen binaphthol derivative through rhodium catalytic hydrogenation
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 technology for the synthesis of octahydrobinaphthol, which is applied in the preparation of organic compounds, chemical instruments and methods, organic chemistry, etc., to achieve the effects of high yield, convenient operation, and simple post-treatment
Inactive Publication Date: 2013-06-05
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
View PDF1 Cites 4 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
However, the synthesis of optically pure octahydrobinaphthol derivatives through catalytic h
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.
Smart Image
Examples
Experimental program
Comparison scheme
Effect test
Embodiment 1
[0029] Embodiment 1: optimization of conditions
[0030] Add cyclooctadiene rhodium chloride (1.3 mg, 0.0025 mmol), substrate 1a (716 mg, 0.25 mmol) to a 10 mL reaction flask in air, MS (50 mg) and isopropanol (3 ml), put the reaction flask into a high-pressure reactor, feed hydrogen at 50 atmospheres, and react at 80° C. for 16 hours. Slowly release hydrogen, remove the solvent, and directly separate the pure product by column chromatography. The reaction formula and ligand structure are as follows:
[0031]
[0032] The enantiomeric excess of the product was determined by chiral liquid chromatography, see Table 1.
[0036] Add cyclooctadiene rhodium chloride (1.3 mg, 0.0025 mmol), substrate 1 (0.25 mmol) to a 10 mL reaction flask in air, MS (50 mg) and isopropanol (3 ml), put the reaction flask into a high-pressure reactor, feed hydrogen at 50 atmospheres, and react at 80° C. for 16 hours. Slowly release hydrogen, remove the solvent, and directly separate the pure product by column chromatography. The reaction formula and ligand structure are as follows, and the reaction formula is as follows:
[0037]
[0038] The enantiomeric excess of the product was determined by chiral liquid chromatography, see Table 2.
[0039] Table 2. Rhodium-catalyzed hydrogenation synthesis of octahydrobinaphthol derivatives 2
[0040]
[0041] The experimental data of each compound are as follows:
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
Login to view more
Abstract
The invention discloses a method of compounding an eight-hydrogen binaphthol derivative through rhodium catalytic hydrogenation. A catalytic system used in the method is rhodium coordination compounds. A reaction is conducted under the conditions that temperatures are in a range of 0-100 DEG C, solvents are different alcohol, the pressure is in a range of (1-100) *1.01325*10<5>Pa, the ratio of zymolyte to catalysts is 100:1, metal precursor used is the rhodium coordination compounds, and additives used are different types of molecular sieves, alumina, aliquat 336, polyvinyl pyrrolidone (PVP) and tetrabutylammonium bromide. Hydrogenation is conducted on an optically pure binaphthol derivative to obtain the corresponding eight-hydrogen binaphthol derivative, wherein enantiomeric excess of the eight-hydrogen binaphthol derivative is kept to be larger than 99%. The method of compounding the eight-hydrogen binaphthol derivative through the rhodium catalytic hydrogenation is simple, convenient and practical to use, good in regioselectivity, and high in productivity. The reaction has green atom economy and is environment-friendly.
Description
technical field [0001] The invention relates to a method for obtaining high-enantiopure octahydrobinaphthol derivatives by hydrogenating a rhodium homogeneous system. Background technique [0002] Chiral octahydrobinaphthol derivatives are important synthetic raw materials in organic catalysis and organic synthesis. 8 -BINOL-based chiral ligands also play an important role in asymmetric synthesis and catalysis [a) McDougal, N.T.; Schaus, S.E.A.J.Am.Chem.Soc.2003, 125, 12094-12095.b) Au -Yeung, T.T.-L.; Chan, S.-S.; Chan, A.S.C.Adv.Synth.Catal.2003, 345, 537-555], however, there is little literature on the synthesis of octahydrobinaphthol derivatives reports. In 1978, the Cram group reported the first case of H 8 -BINOL synthesized, they use expensive PtO 2 As a catalyst, 94% yield can be obtained by reacting at room temperature for 7 days, and the configuration of the product is completely maintained [Cram, D.J.; Helgeson, R.C.; Peacock, S.C.; Kaplan, L.J.; Domeier, L.A....
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
IPC IPC(8): C07C39/14C07C37/00
Inventor 周永贵陈木旺余长斌
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
Login to view more 
Login to view more