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Prepn of chiral compounds S-(+)-and R-(-)-1-(alpha-aminobenzyl)-2-naphthol

A technology of aminobenzyl and naphthol is applied in the field of optical separation to prepare chiral compounds with high optical purity, and can solve the problems that the separation method cannot be completely overcome, the chemical yield is low, and the separation is incomplete.

Inactive Publication Date: 2002-05-15
NANJING UNIV
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  • Summary
  • Abstract
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Problems solved by technology

However, the fact that this compound has not received more research and application clearly implies that there may be insurmountable difficulties in its resolution method.
When we carried out the resolution of optical isomers of (±)-1-(α-aminobenzyl)-2-naphthol (1) according to the two methods reported in the literature, we found that in addition to the chemical yield In addition to the shortcomings of low and incomplete resolution, it is also accompanied by the generation of decomposition products

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0015] S-(+)-1-(α-aminobenzyl)-2-naphthol complex with L-(+)-tartaric acid (S-L-2) and (R)-(-)-1-(α-amino Preparation of benzyl)-2-naphthol complex with D-(-)-tartaric acid (R-D-2).

[0016] Under stirring at room temperature, a solution of L-(+)-tartaric acid (32.5 g, 217 mmol) in acetone (1000 mL) was added dropwise to (±)-1-(α-aminobenzyl)-2-naphthol (1 , 50g, 201mmol) and acetone (500mL) generated white cloudy liquid. During the dropwise addition, the system first turned to clear, and then a white precipitate began to form. After the mixture was stirred at room temperature for 12 hours, the resulting white solid was filtered off, and the filter cake was washed with acetone (2×100 mL) and dried to obtain 39.4 g (95.5%, calculated as a single isomer) of (S)- (+)-1-(α-aminobenzyl)-2-naphthol complex with L-(+)-tartaric acid (S-L-2). Contain (R)-(-)-1-(α-aminobenzyl)-2-naphthol and L-(+)-tartaric acid complex (R-L-2) in the acetone mother liquor after merging, in embodiment...

Embodiment 2

[0019] High optical purity (S)-(+)-1-(α-aminobenzyl)-2-naphthol (S-1) and high optical purity (R)-(-)-1-(α-aminobenzyl )-2-naphthol (R-1) preparation.

[0020] At room temperature, the solution of the S-L-2 complex solid (39.4g) obtained in Example 1, saturated sodium carbonate solution (400mL) and water (400mL) was fully stirred for 45 minutes, then diethyl ether (800mL, 2 ×100mL) extracted three times. The combined extracts were dried over anhydrous sodium sulfate, concentrated to about 100 mL, and left at 0°C for 2 hours. The resulting crystals were filtered off and washed with a small amount of ether to obtain 20.7 g (84%) of (S)-(+)-1-(α-aminobenzyl)-2-naphthol (S-1) as colorless needles crystals. In the presence of the solvating chiral reagent R-(-)-3,5-dinitro-N-(1-phenylethyl)benzamide, the 1H NMR spectrum of this compound shows an optical purity of 99% ee . The compound has m.p.133-134°C, [α] 25 D =+58.2°(C 6 h 6 , c=1); IR(KBr): v 3360, 3290, 3010, 2550, 162...

Embodiment 3

[0023](R)-(-)-1-(α-aminobenzyl)-2-naphthol complex with L-(+)-tartaric acid (R-L-2) and (S)-(+)-1-(α Preparation of complex (S-D-2) of -aminobenzyl)-2-naphthol with D-(-)-tartaric acid.

[0024] Concentrate the acetone mother liquor obtained by filtering out complex S-L-2 in Example 1 to about 100 mL, and then place it at room temperature for 2 hours. The precipitated white solid was filtered and dried to obtain 27.4g (66%, calculated as a single isomer) of (R)-(-)-1-(α-aminobenzyl)-2-naphthol and L-(+ )-tartaric acid complex (R-L-2).

[0025] Under the above conditions, when using the acetone mother liquor after complex R-D-2 was filtered out, (S)-(+)-1-(α-aminobenzyl)-2-naphthol and D-( -)-Tartrate complex (S-D-2) as a white solid.

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Abstract

A preparation method for S-(+)-1-(alpha-aminobenzyl)-2-naphthol or R-(-)-1-(alpha-aminobenzyl)-2-naphthol mainly includes the following steps: A. under room temp., racemized (minus or plus)-1-(alpha-aminobenzyl)-2-naphthol is added with acetone and mixed, L-(+)-tartaric acid is added, mixing is continued until white solid is completely deposited, and then it is filtered to obtain S-(+)-1-(alpha-aminobenzyl)-2-naphthol and complex substance S-L-2 solid of L-(+)-tartaric acid; B. the obtained two components in step A are mixed and analyzed in sodium carbonate solution, and extracted with ethyl ether. The merged liquid extracts after being concentrated have the residual liquid obtained and stood still under low-temp., and the high-optical purity crystal of S-(+)-1-(alpha-aminobenzyl)-2-naphthol (S-1) is precipitated.

Description

1. Technical field [0001] The present invention relates to the method for preparing chiral compound with high optical purity by optical resolution, specifically the method for preparing S-(+)- and R-(-)-1-(α-aminobenzyl)-2-naphthol . 2. Background technology [0002] Chiral 1,2- and 1,3-amino-hydroxyl compounds have proven to be an important class of ligands for metal-catalyzed asymmetric synthesis (see K.Soai, S.Niwa, Chem.Rev., 1992, 92 , 833.). Among the various aminoalcohol ligands that have been successfully developed in the past, the vast majority start from chiral source compounds (seeing D.J.Ager, I.Prakash, D.R.Schaad, Chem.Rev., 1996,96,835. ). However, the design and synthesis of amino-hydroxyl chiral ligands of non-chiral sources have become an important content and development trend in current asymmetric synthesis research (see a.A.Vidal-Ferran, A.Moyano, M.A.Pericas, A.Riera , J. Org. Chem., 1997, 62, 4970.b. C. Bolm, K. Muniz-Fernandez, A. Seger, G. Raabe,...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C213/10C07C215/50
Inventor 胡跃飞陆军许学农王存德王少仲胡宏纹
Owner NANJING UNIV
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