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Method for preparing antimer (R)or (S)-1,1'-bi-2-naphthol

A naphthol and crystallization technology, applied in the field of chiral compound preparation chemistry, can solve problems such as high preparation cost, and achieve the effects of short preparation period, high yield and low cost

Inactive Publication Date: 2006-02-15
WUHAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

As far as the preparation of enantiopure (R)- or (S)-1,1'-bi-2-naphthol is concerned, chiral quaternary ammonium salts derived from cinchona base and other chiral compounds are often used As enantioselective inclusion agent (D.Cai, L.D.Hughes, T.R.Verhoeven, P.J.Reider, Tetrahedron Lett.1995,36,7991; K.Tanaka, T.Okada, F.Toda, Angew.Chem., Int.Ed. 1993, 32, 1147; F. Toda, K. Tanaka, Z. Stein, I. Goldberg, J. Org. Chem. 1994, 59, 5748; Y. Wang, J. Sun, K. L. Ding, Tetrahedron 2000, 56, 4447; M.Kwashima, A.Hirayama, Chem.Lett.1990, 2299; M.Kwashima, R.Hirata, Bull.Chem.Soc.Jpn.1993, 66, 2002.), high preparation cost

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] Threo(1S,2S)-2-dimethylamino-1-(p-nitrophenyl)-1,3-propanediol and benzyl chloride were refluxed in acetone for 24 hours, then cooled and filtered to obtain (1S, 2S)-1,3-dihydroxy-1-(p-nitrophenyl)-2-(N-benzyl-N,N-dimethyl)propyl ammonium salt crude product; the mother liquor was concentrated to obtain the second product; The crude product was combined with the second product, and recrystallized with ethanol to obtain white needle-like crystals; the yield was 65%; m.p.184-187°C; 1 H NMR (d 6 -DMSO): δ3.21(s, 3H), 3.26(s, 3H), 3.73(d, 1H), 3.85(d, 1H), 4.97-5.13(m, 2H), 5.55(t, 1H), 5.89(s, 1H), 7.27(d, 1H), 7.54(d, 3H), 7.65(d, 2H), 7.76(d, 2H), 8.26(d, 2H); MS(FAB): 331(M + -Cl, 100), 315 (M + -Cl-O, 10), 239 (M + -PhCH 2 Cl-1, 8), 91 ([M PhCH2 ] + , 95).

[0020] The racemic 1,1'-bi-2-naphthol and the chiral clathrate prepared above were chlorinated (1S, 2S)-1,3-dihydroxy-1-(p-nitrophenyl)- 2-(N-benzyl-N, N-dimethyl) propylammonium salt is dissolved in aceton...

Embodiment 2

[0023] According to the method of Example 1, racemic 1,1'-bi-2-naphthol and (1S,2S)-1,3-dihydroxy-1-(p-nitrogen chloride) were mixed in a molar ratio of 1:0.5 phenyl)-2-(N-benzyl-N, N-dimethyl) propylammonium salt in methanol (the amount of methanol is racemic 1,1 '-linked-2-naphthol weight of 5- 20 times), mixed in, heated to dissolve and then cooled to precipitate clathrate crystals. This crystal was stirred in dilute hydrochloric acid and chloroform mixed solution, separated the organic phase, dried, evaporated, and recrystallized to give (S)-1,1'-bi-2-naphthol block crystals, yield, About 80%, m.p 206-208°C, 100% ee. The mother liquor after separation of this crystal was treated according to the procedure of Example 1 to obtain massive, colorless and transparent (R)-1,1'-bi-2-naphthol crystals with a yield of 80-85%, m.p.206 -208°C, [α] D 20 =+35.4 (c=1 in THF), 100% ee.

Embodiment 3

[0025]According to the method of Example 1, racemic 1,1'-bi-2-naphthol and (1S,2S)-1,3-dihydroxy-1-(p-nitrogen chloride) in a molar ratio of 1:3 phenyl)-2-(N-benzyl-N,N-dimethyl)propylammonium salt in a mixture of tetrahydrofuran and water (the amount of tetrahydrofuran is racemic 1,1'-bi-2-naphthol about 15 times the weight), and then heated to dissolve and then cooled to precipitate clathrate crystals. This crystal is stirred in the mixed solution of sodium hydroxide solution and benzene, and the organic phase is separated, dried, evaporated, and recrystallized to give (S)-1,1'-bi-2-naphthol block crystals, Yield, 82%, m.p 206-208°C, 100% ee. After the clathrate crystals were separated, the mother liquor was concentrated and cooled to room temperature, and massive, colorless and transparent (R)-1,1'-bi-2-naphthol crystals were precipitated, with a yield of about 85%, m.p.206-208 °C, [α] D 20 ==+35.4 (c=1 in THF), 100% ee.

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Abstract

The invention relates to a process for preparing chiral (R)- or (S)-1,1'-bi-2-naphthol, which comprises mixing racemic or non-racemic 1,1'-bi-2-naphthol and chiral inclusion agent by the mol ratio of 1.0:0.5-3.0 in organic polar solvent, heating, dissolving and cooling down for evolution of inclusion compound and crystallizing, decomposing the inclusion compound crystallization to obtain (S)-1,1'-bi-2-naphthol, evaporating the mother liquor, crystallizing the purifying the residue to obtain (R)-1,1'-bi-2-naphthol, the chiral inclusion agent is chloride (1S,2S)-1,3-dihydroxyl-1(nitrophenyl)-2-(N-benzyl-N,N-dimethyl) propanaminiumchloride.

Description

technical field [0001] The invention describes a method for preparing 100% enantiomeric excess (R)- or (S)-1,1'-bi-2-naphthol with high yield by supramolecular chemistry, and belongs to the field of chiral compound preparation chemistry. Background technique [0002] Enantiopure (R)- or (S)-1,1'-bi-2-naphthols have C 2 Important chiral compounds with symmetry axes, they are not only widely used in stoichiometric and catalytic asymmetric reactions as general-purpose chiral ligands and auxiliary agents in asymmetric synthesis, but also they are used to prepare other 1,1′- Starting material for chiral compounds of bi-2-naphthalene fragments. [0003] The preparation methods of photoactive 1,1'-bi-2-naphthol can be divided into two categories, namely racemate resolution and enantioselective synthesis. As far as the resolution method is concerned, there are mainly: diastereomer separation method (cyclic phosphate method, cycloborate method, spiroborate method, etc.), enantiosel...

Claims

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Application Information

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IPC IPC(8): C07C39/14C07C37/86
Inventor 单自兴哈伍族
Owner WUHAN UNIV
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