CN1264699A - High-optical-purity dinaphthdiol monomenthyl carbonate and its preparing process - Google Patents
High-optical-purity dinaphthdiol monomenthyl carbonate and its preparing process Download PDFInfo
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- CN1264699A CN1264699A CN 99127581 CN99127581A CN1264699A CN 1264699 A CN1264699 A CN 1264699A CN 99127581 CN99127581 CN 99127581 CN 99127581 A CN99127581 A CN 99127581A CN 1264699 A CN1264699 A CN 1264699A
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- monomenthyl
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Abstract
A process for preparing an organic compound with optical activity includes such steps as reaction of racemic dinaphthdiol on (-)-menthyl chlorocarbonate to obtain the diasteroeoisomeric mixttr 3 of 1,1'-dinaphthyl-2,2'-diphenol-mono-[(-)-methyl] carbonate, and classifiable crystallizing to split two isomers apart from each other to obtain dextro-isomer 3a and laevo-isomer 3b with optical purity not lower than 99%. They can be used to prepare high-optical-purity 1,1'-dinaphthyl-2,2'-diphenol and other important chiral catalyst ligand of dinaphthalene. Its advantages are simple process and low cost.
Description
The present invention relates to a kind of optically active organic compound and preparation method thereof.
Optically pure 1,1 '-the naphthyl naphthalene compound is auxiliary agent, catalyzer or a catalyst ligand important in the asymmetric catalysis synthesis, is widely used in the important organic synthesis such as asymmetric reduction, asymmetric hydrogenation, asymmetric isomerization.The preparation of this compounds and application are Synthetic Organic Chemistry active research fields very in recent years.
Purpose of the present invention aim to provide a kind of new high optically pure 1,1 '-naphthyl naphthalene compound-1,1 '-dinaphthalene diphenol list Meng Ji carbonic ether and preparation method thereof.This compound can be used for producing 1,1 of high-optical-purity '-dinaphthalene-2,2 '-diphenol and other important naphthyl naphthalene chiral catalyst part, in particular for prepare 2,2 '-the optically active naphthyl naphthalene catalyst ligand of asymmetric replacement.
The said high-optical-purity dinaphthdiol monomenthyl carbonic ether of the present invention is meant dextrorotation and left-handed 1,1 '-dinaphthalene-2,2 '-diphenol-list-[(-)-Meng Ji] carbonic ether, be called for short 3a and 3b below, its English name is 1,1 '-binaphthyl-2,2 '-diol-mono-[(-)-and menthyl] carbonate.3a has identical molecular formula with 3b, determines that it is C through the analysis of monocrystalline X-ray diffraction
31H
32O
4, molecular weight is 468.56.Its structural formula is respectively:
3a is diastereomer with 3b and has different physical propertiess.Wherein the fusing point of 3a is 203.5-205 ℃, optical value [α]
D 20Be+27.6 (C1.2, CH
2Cl
2); The fusing point of 3b is 173-174 ℃, optical value [α]
D 20Be-121.6 (C1.2, CH
2Cl
2).
The said dextrorotation 1,1 of the present invention '-dinaphthalene-2,2 '-diphenol-list-[(-)-Meng Ji] carbonic ether 3a and left-handed 1,1 '-dinaphthalene-2,2 '-chemical equation of the preparation process of diphenol-list-[(-)-Meng Ji] carbonic ether 3b is as follows:
Its concrete steps are: racemic dinaphthalene diphenol (±)-1 is dissolved in low polar anhydrous, preferably in methylene dichloride, ethyl acetate or the ether etc., is mixed with 0.1～0.5M, preferably the solution of 0.1～0.3M; Toward wherein adding 1.2～2.0 molar equivalents, preferably the organic amine acid binding agent of 1.5 molar equivalents.Said organic amine acid binding agent can be selected from tertiary amines such as triethylamine, diisopropyl ethyl amine; Said mixture is chilled to-20 ℃～10 ℃, preferably-10 ℃～-5 ℃, acylation reaction catalyst right-N, the N dimethylamine yl pyridines exists down, under agitation toward wherein adding 0.9～1.15, preferably (-) of 1.0～1.05 molar equivalents-Meng Ji chlorinated carbonates 2, continue to stir 2～3 hours under uniform temp; Toward wherein adding an amount of water, tell organic phase, water is used and is reacted employed homogeneous solvent extraction.Merge organic phase, add the siccative drying, refilter and remove siccative, filtrate is under reduced pressure steamed and is desolventized, the gained solid crude product mixed solvent crystallization of ethyl acetate and stable hydrocarbon such as hexane or sherwood oil.When the ratio of ethyl acetate and stable hydrocarbon is separated out 3a during in (8: 1)～(5: 1), the two ratio is transferred to (1: 1)～(1: 4) then separate out 3b.
The present invention utilizes racemic 1,1 '-dinaphthalene-2,2 '-diphenol [(±)-1] and 2 reactions of (-)-Meng Ji chlorinated carbonates, form [(+)-and (-)-1,1 '-dinaphthalene-2,2 '-diphenol]-non-enantiomer mixture 3 of list-[(-)-Meng Ji] carbonic ether, the method by fractional crystallization splits two isomer then, obtains high optically pure compound 3a and 3b.3a and 3b can be used for producing 1 of high-optical-purity, 1 '-dinaphthalene-2,2 '-diphenol [(+)-1 and (-)-1], they are reagent, catalyzer or catalyst ligands important in the asymmetric catalysis synthesis, are widely used in the important building-up reactionss such as asymmetric reduction reaction, asymmetric hydrogenation, asymmetric isomerization, asymmetric [4+2] cycloaddition.3a and 3b as the high optical purity 1,1 of single-ended protection '-dinaphthalene-2,2 '-diphenol, also can be advantageously used in the preparation of 2,2 '-the important chirality naphthyl naphthalene catalyst ligand of asymmetric replacement, as 2-(diphenyl phosphine)-2 '-methoxyl group-1,1 '-dinaphthalene (MOP) etc.Preparation method of the present invention is simple, economical, be suitable for suitability for industrialized production.
Below by embodiment the present invention is described in further detail.
Embodiment 1: under agitation with 5.72 gram racemizes 1, and 1-dinaphthalene-2,2 '-diphenol (±-1) is dissolved in 100 milliliters of exsiccant methylene dichloride, toward wherein adding 5.54 milliliters of triethylamines and 50 milligrams of right-N, N dimethylamine yl pyridines.After being cooled to-10 ℃, under stirring fast, restrain (-)-Meng Ji chlorinated carbonates 2 toward wherein dripping 4.36.Dropwise the back and continue to stir 3 hours to reacting completely at-10 ℃.In reaction mixture, add 100 ml waters then, stir and make the solid dissolving.Tell organic layer, water layer is with 100 milliliters of dichloromethane extractions.Merge organic layer, use anhydrous magnesium sulfate drying.Remove by filter siccative, filtrate is under reduced pressure steamed and is desolventized, and the gained solid crude product is with 7: 1 the ethyl acetate and the mixed solvent crystallization of hexane.The crystal of separating out is with a small amount of cold ethyl acetate washing, after the drying dextrorotation 1,1 '-dinaphthalene-2,2 '-diphenol-list-[(-)-Meng Ji] carbonic ether 3a, output 4.3 restrains, fusing point 203.5-205 ℃, optical value [α]
D 20+ 27.6 (C1.2, CH
2Cl
2); Ultimate analysis: measured value (%): C, 78.97; H, 6.86; C
31H
32O
4Calculated value (%): C, 79.45; H, 6.88; IR (KBr compressing tablet) (cm
-1): 3490 (s, μ
O-H), 3060 (m, μ
C=C-H), 1739 (s, μ
C=O);
1H-NMR (CDCl
3, 300MHz, TMS=0ppm) characteristic peak: 0.488,0.689 and 0.821ppm (each 3H, doublet) be the proton of three methyl among the Meng Ji, 5.21ppm (1H, unimodal) is the phenolic hydroxyl group proton, 6.98-8.21ppm (12H, multiplet) is the naphthalene nucleus proton.Through high pressure liquid chromatographic analysis, the optical purity of 3a＞99%.Add the ratio to 1 that hexane is regulated two solvents: separate out after 2 left-handed 1,1 '-dinaphthalene-2,2 '-diphenol-list-[(-)-Meng Ji] carbonic ether 3b.Crystal gets product 4.0 grams with a small amount of cold ethyl acetate washing after the drying, fusing point is 173-174 ℃, optical value [α]
D 20-121.6 (C1.2, CH
2Cl
2); Ultimate analysis: measured value (%): C, 79.00; H, 6.85; C
31H
32O
4Calculated value (%): C, 79.45; H, 6.88; IR (KBr compressing tablet) (cm
-1): 3490 (s, μ
O-H), 3060 (m, μ
C=C-H), 1740 (s, μ
C=O);
1H-NMR (CDCl
3, 300MHz, TMS=0ppm) characteristic peak: 0.598,0.697 and 0.886ppm (each 3H, doublet) be three methyl protons among the Meng Ji, 5.33ppm (1H, unimodal) is the phenolic hydroxyl group proton, 7.08-8.14ppm (12H, multiplet) is the naphthalene nucleus proton.High pressure liquid chromatographic analysis is determined its optical purity＞99%.
Embodiment 2: operation is with embodiment 1, and changing temperature of reaction is 10 ℃, gets the 3a3.9 gram, optical purity＞99%; 3b3.5 gram, optical purity＞97%, and have～10% 1,1 '-two Meng Ji carbonic ethers form.
Embodiment 3: operation is with embodiment 1, with 6.96 milliliters of triethylamines that replace among the embodiment 1 of diisopropyl ethyl amine.Get the 3a4.1 gram, optical purity＞99%; 3b 3.8 grams, optical purity＞99%.
Embodiment 4: under agitation with 2.88 gram racemizes 1,1 '-dinaphthalene-2,2 '-diphenol (±-1) is dissolved in 80 milliliters of exsiccant ether, toward wherein adding 2.8 milliliters of triethylamines and 30 milligrams of right-N, N dimethylamine yl pyridines.After being cooled to-10 ℃, toward wherein dripping 2.2 gram (-)-Meng Ji chlorinated carbonates 2.Dropwising the back continues to stir 2 hours to reacting completely at-10 ℃.In reaction mixture, add 50 ml waters subsequently, stir and make the solid dissolving.Tell organic layer, twice of extracted with diethyl ether of water layer.Merge organic layer, use anhydrous magnesium sulfate drying.Remove by filter siccative, filtrate is under reduced pressure steamed and is desolventized, gained solid crude product ethyl acetate/petroleum ether mixed solvent crystallization.When being 7: 1, ethyl acetate/petroleum ether gets the 3a2.1 gram, optical purity＞99%; The ratio of regulating two solvents is to get 3b1.9 gram, optical purity＞99% at 1: 3 o'clock.
Embodiment 5: operation replaced ether with embodiment 4 with 80 milliliters of exsiccant ethyl acetate, in-20 ℃ of reactions 3 hours.Get the 3a2.0 gram, optical purity＞99%; 3b1.7 gram, optical purity＞99%.
Embodiment 6: under agitation with 2.34 gram dextrorotation 1,1 '-dinaphthalene-2,2 '-diphenol-list-[(-)-Meng Ji] carbonic ether 3a is dissolved in 25 milliliters of exsiccant methyl alcohol, restrains solid sodium methylates toward wherein adding 1.08.Reaction mixture at room temperature stirs 5 hours to reacting completely.In reaction mixture, add 15 milliliters of saturated aqueous ammonium chlorides and 50 milliliters of ether then, be acidified to pH＜5 with the 2mol/L aqueous hydrochloric acid.Tell organic layer, water layer is with twice of 25 milliliters of extracted with diethyl ether.Merge organic layer, use anhydrous sodium sulfate drying.Remove by filter siccative, filtrate is under reduced pressure steamed and is desolventized, and the gained solid crude product is with ether/sherwood oil mixed solvent crystallization, dextrorotation 1,1 '-dinaphthalene-2,2 '-diphenol 1.18 grams, fusing point 209-210 ℃, optical value [α]
D 20+ 35.2 (C1, THF).High pressure liquid chromatographic analysis is determined its optical purity＞99%.
Claims (7)
1. high-optical-purity dinaphthdiol monomenthyl carbonic ether, it is characterized in that said high-optical-purity dinaphthdiol monomenthyl carbonic ether be dextrorotation and left-handed 1,1 '-dinaphthalene-2,2 '-diphenol-list-[(-)-Meng Ji] carbonic ether, molecular formula is C
31H
32O
4, molecular weight is 468.56, its structural formula is respectively:
Wherein the fusing point of 3a is 203.5-205 ℃, optical value [α]
D 20Be+27.6 (C1.2, CH
2Cl
2); The fusing point of 3b is 173-174 ℃, optical value [α]
D 20Be-121.6 (C1.2, CH
2Cl
2).
2. the preparation method of the described high-optical-purity dinaphthdiol monomenthyl carbonic ether of claim 1 is characterized in that chemical equation is:
Its reactions steps is: (1) is dissolved in racemic dinaphthalene diphenol (±)-1 in the low polar anhydrous, is mixed with the solution of 0.1～0.5M; (2) add the organic amine acid binding agent of 1.2～2.0 molar equivalents in the solution; (3) said mixture is chilled to-20 ℃～10 ℃, acylation reaction catalyst right-N, the N dimethylamine yl pyridines exists down, stirs (-)-Meng Ji chlorinated carbonates 2 that adds 0.9～1.15 molar equivalent down, continues to stir 2～3 hours under uniform temp; (4) through extraction, dry, filter, steam and desolventize the mixed solvent crystallization that back gained solid crude product is used ethyl acetate and stable hydrocarbon such as hexane or sherwood oil.When the ratio of ethyl acetate and stable hydrocarbon is separated out 3a during in (8: 1)～(5: 1),, the two ratio then separates out 3b when transferring to (1: 1)～(1: 4).
3. the preparation method of high-optical-purity dinaphthdiol monomenthyl carbonic ether as claimed in claim 2, the concentration that it is characterized in that dinaphthalene diphenol (±)-1 solution in the step 1 is 0.1～0.3M.
4. the preparation method of high-optical-purity dinaphthdiol monomenthyl carbonic ether as claimed in claim 2 is characterized in that the organic amine acid binding agent described in the step 2 is triethylamine, diisopropyl ethyl amine.
5. the preparation method of high-optical-purity dinaphthdiol monomenthyl carbonic ether as claimed in claim 2, the consumption that it is characterized in that organic amine acid binding agent in the step 2 is 1.5 molar equivalents.
6. the preparation method of high-optical-purity dinaphthdiol monomenthyl carbonic ether as claimed in claim 2, the temperature of reaction that it is characterized in that step 3 are-10～-5 ℃.
7. the preparation method of high-optical-purity dinaphthdiol monomenthyl carbonic ether as claimed in claim 2, the add-on that it is characterized in that (-) in the step 3-Meng Ji chlorinated carbonates 2 is the 1.0-1.05 molar equivalent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105115430A (en) * | 2015-05-26 | 2015-12-02 | 雷艳梅 | Point-grid reflection-type chemical liquid applying uniformity detection method and device |
| CN105732404A (en) * | 2016-03-30 | 2016-07-06 | 杭州百合科莱恩颜料有限公司 | Binaphthalenediol compound and application thereof |
-
1999
- 1999-12-24 CN CN99127581A patent/CN1085655C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105115430A (en) * | 2015-05-26 | 2015-12-02 | 雷艳梅 | Point-grid reflection-type chemical liquid applying uniformity detection method and device |
| CN105115430B (en) * | 2015-05-26 | 2016-08-31 | 山东建筑大学 | A kind of some grid transmission-type chemical liquid smears uniformity detecting method and device |
| CN105732404A (en) * | 2016-03-30 | 2016-07-06 | 杭州百合科莱恩颜料有限公司 | Binaphthalenediol compound and application thereof |
| CN105732404B (en) * | 2016-03-30 | 2017-08-22 | 杭州百合科莱恩颜料有限公司 | Binaphthol class compound and application thereof |
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