CN101891716A - Synthesis method of S-beta-hydroxy-gamma-butyrolactone - Google Patents
Synthesis method of S-beta-hydroxy-gamma-butyrolactone Download PDFInfo
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- CN101891716A CN101891716A CN 201010192804 CN201010192804A CN101891716A CN 101891716 A CN101891716 A CN 101891716A CN 201010192804 CN201010192804 CN 201010192804 CN 201010192804 A CN201010192804 A CN 201010192804A CN 101891716 A CN101891716 A CN 101891716A
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- malic acid
- methyl
- butyrolactone
- gamma
- hydroborate
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Abstract
The invention discloses a synthesis method of S-beta-hydroxy-gamma-butyrolactone, comprising the steps of: synthesis of L-dimethyl ester malate, synthesis of 3, 4-dihydroxybutyric acid methyl ester, synthesis of S-hydroxy-gamma-butyrolactone and the like.The synthesis method mainly adopts BiBr3/ hydroborate/ lower alcohol reducing system to selectively reduce monoester into alcohol, so that borane dimethyl sulfide composite which is combustible and explosive, is not easily stored and has high price in the prior art is avoided being used. The synthesis method of the S-beta-hydroxy-gamma-butyrolactone is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of synthetic method of compound, specifically a kind of method of synthetic (S)-beta-hydroxy-gamma-butyrolactone.
Background technology
The S-beta-hydroxy-gamma-butyrolactone is very important chiral medicinal intermediate
1,2, its synthetic attention that has more and more caused chemist.Traditional technology mainly contains: by the L MALIC ACID esterification, and reduction, cyclization
3-6Perhaps by carbohydrate as the oxidation of lactose, maltose
7-9, finally synthetic S-beta-hydroxy-gamma-butyrolactone.Regioselectivity when preceding most two ester groups of a kind of method are reduced is not high, and impurity is more, has caused yield lower; A kind of method in back also causes very difficulty of product purification because the by product that produces is complicated in oxidising process.Therefore, above technology all is difficult to realize industrialization.
The synthetic method of synthetic S-hydroxyl-gamma-butyrolactone that using value is arranged of having reported is as follows:
The synthetic route condition of this method is gentle, its limitation be this route adopted inflammable and explosive, be difficult for preserving, expensive borine dimethyl sulphide mixture, and used solvent is the tetrahydrofuran (THF) of anhydrous and oxygen-free, this is totally unfavorable to industrial production.
Reference
[1]Hartmuth?C.K.，Youssef?L.B.，Sharpless?K.B.Enantiomerically?pureβ，γ-epoxyesters?from?β-hydroxylactones：synthesis?of?β-hydroxyesters?and?(-)-GABOB[J].Tetrahedron，1990，46(12)：4277-4282.
[2]Kim?E.E.，Baker?C.F.，Dwyer?M.D.，et?al.Crystal?structure?of?HIV-1protease?in?complex?with?VX-478，a?potent?and?orally?bioavailableinhibitor?of?the?enzyme[J].Am.Chem.Soc.，1995，117(3)：1181-1182.
[3]Guanti?G.，Banf?I.，Naiisano?E.Stereoselective?preparation?ofsynthetic?equivalents?of?2-deoxy-2-amino-?and3-deoxy-3-aminotetroses?from?malicacid.Application?to?the?synthesisof?C
18-D-ribo-phytosphingosine[J].Tetrahedron?Lett.，1989，30(40)：5507-5510.
[4]Saito?S.，Hassegawa?T.，Inaba?M.，et?al.Combination?ofborane-dimethyl?sulfide?complex?with?catalytic?sodiumtetrahydroborate?as?a?selective?reducing?agent?for?α-hydroxy?esters，versatile?chiral?building?block?from?(s)-(-)-malic?acid.Chem.Lett.，1984，1389-1392.
[5]Hofmann?R.W.，Schlapbaaeh?A.Allylboration-reactions，the?key?toa?shortsynthesis?of?benzoyl-pedamide[J].Tetraheseon，1992，48(11)：1959-1968.
[6]Falck?J.R.，Lumin?S.，lee?S.，et?al.Enantiospecific?synthesis?of17-and?18-hydroxyeicosatetraenoic?acids，cytochrome?P450arachidonate?metabolites[J].Tetrahedron?Lett.，1992，33(34)：4893-4896.
[7]Moil?K.，Takigawa?T.，Matsuo?T.Synthesis?of?optically?active?formsof?ipsdienol?and?ipsenol：The?pheromone?components?of?ips?barkbeetles[J].Tetrahedron，1979，35(8)：933-940.
[8]Huang?G.，Hollingswor?th?R.I.Synthesis?of?achiral?phospholipase-Cand?D?insensitive?membrane?probe?with?excimer?emission?properties[J].Tetrahedron，1998，54(8)：1355-1360.
[9]Tanaka?A.，Yamashita?K.A?Novel?Synthesis?of(R)-and(S)-4-Hydroxytetrahydrofuran-2-ones[J].Synthesis，1987，6：570-572.
Summary of the invention
The present invention is directed to the existing shortcoming of above-mentioned synthetic method, employing BiBr is provided
3The single ester to alcohol of/hydroborate/lower alcohol reduction system selective reduction is exempted inflammable and explosive, as to be difficult for preservation, expensive borine dimethyl sulphide mixture use, is fit to the method for the S-hydroxyl-gamma-butyrolactone of suitability for industrialized production.
Technical scheme of the present invention
Synthetic route of the present invention is as follows:
Wherein: a.AcCl, MeOH;
B.BiBr
3/ hydroborate/lower alcohol;
C. mineral acid, THF refluxes.
A kind of synthetic method of S-beta-hydroxy-gamma-butyrolactone comprises the steps:
(1), the L MALIC ACID dimethyl ester is synthetic
Methyl alcohol and Acetyl Chloride 98Min. add the solid L MALIC ACID after mixing under 0 ℃, rising to room temperature to solid dissolves, react 12h again, resistates is dissolved in the ethyl acetate, and organic phase is washed with saturated sodium bicarbonate, water and saturated nacl aqueous solution, drying concentrates, and gets the product intermediate;
The gained intermediate is dissolved among the THF again, drips tetrabutyl ammonium fluoride again under 0 ℃, the mixture of gained stirred 3 hours down in 0 ℃, the ether dilution, organic phase water, saturated nacl aqueous solution washing, drying concentrates, colourless oil liquid L MALIC ACID dimethyl ester;
The volume or the mol ratio of above-mentioned methyl alcohol, Acetyl Chloride 98Min. and solid L MALIC ACID, i.e. methyl alcohol: Acetyl Chloride 98Min.: the solid L MALIC ACID is 200ml～500ml: 5ml～10ml: 0.2mol; Be preferably 300ml: 10ml: 0.2mol;
Wherein the consumption of THF and tetrabutyl ammonium fluoride is pressed L MALIC ACID calculating, and THF: tetrabutyl ammonium fluoride: L MALIC ACID is 10ml～20ml: 2.5mmol～5.0mmol: 1mol; Be preferably 12.5ml: 3mmol: 1mol;
(2), 3,4-dihydroxyl methyl-butyrate synthetic
With the L MALIC ACID dimethyl ester of step (1) gained by BiBr
3, reaction generates 3 in the reduction system formed of hydroborate, lower alcohol, 4-dihydroxyl methyl-butyrate, reaction finishes the back removes solid filtering earlier, concentrate then 3,4-dihydroxyl methyl-butyrate;
Described lower alcohol is a methyl alcohol, and also available ethanol, propyl alcohol, Virahol or the trimethyl carbinol are equal to alternative;
Described hydroborate is POTASSIUM BOROHYDRIDE or sodium borohydride;
Wherein by BiBr
3, BiBr in the reduction system formed of hydroborate, lower alcohol
3, hydroborate and lower alcohol mole 1: 2～5: 2～5; Be preferably 1: 3: 3;
Wherein the L MALIC ACID dimethyl ester of step (1) gained with by BiBr
3, the reduction system formed of hydroborate, lower alcohol the quality proportioning, i.e. L MALIC ACID dimethyl ester: by BiBr
3, the reduction system formed of hydroborate, lower alcohol is 1: 2～5, is preferably 1: 2;
(3), S-hydroxyl-gamma-butyrolactone is synthetic
With step (2) gained 3,4-dihydroxyl methyl-butyrate is under the catalysis of mineral acid, and control reaction temperature is 60 ℃, and the reaction times is 2 hours, promptly gets cyclization and generates S-hydroxyl-gamma-butyrolactone;
Described mineral acid is a sulfuric acid, and also available hydrochloric acid, nitric acid etc. substitute;
Wherein step (2) gained 3, the quality proportioning of 4-dihydroxyl methyl-butyrate and mineral acid, and promptly step (2) gained 3, and 4-dihydroxyl methyl-butyrate: mineral acid is 1: 5～10, is preferably 1: 10.
Beneficial effect of the present invention
The outstanding feature of synthetic route provided by the invention is that with a kind of new reduction system selective reduction L MALIC ACID dimethyl ester be glycol, has exempted inflammable and explosive, difficult preservation, expensive borine dimethyl sulphide mixture.Can be used for large-scale industrial production.Raw materials used cheap, be suitable for the application of suitability for industrialized production.
Embodiment
Below by embodiment the present invention is further set forth, but do not limit the present invention.
Embodiment 1
A kind of synthetic method of S-beta-hydroxy-gamma-butyrolactone comprises the steps:
(1), the L MALIC ACID dimethyl ester is synthetic
Under 0 ℃, Acetyl Chloride 98Min. (10ml) slowly adds in the methyl alcohol (300ml).After dripping off, (26.8g 0.2mol), slowly rises to room temperature, stirs 12h to add L MALIC ACID.Concentrate methyl alcohol, resistates is dissolved in the 250ml acetoacetic ester, and organic phase is washed with saturated sodium bicarbonate, water and saturated nacl aqueous solution, and drying concentrates, and gets intermediate.Intermediate is dissolved among the 2.5mlTHF, 0 ℃ drip down tetrabutyl ammonium fluoride (1.0M, 0.6ml, 0.6mmol), mixture stirred 3 hours down for 0 ℃, the dilution of 15ml ether, organic phase water, saturated nacl aqueous solution washing, drying, concentrate, obtain colourless oil liquid 27g, productive rate 92%.
[α]
D 25＝-7.50(c?3.45，MeOH)；
1H?NMR(CDCl
3，300MHz)：2.85(2H，m)，3.72(3H，s)，3.82(3H，s)，4.53(2H，m)ppm；
MS(EI，m/z)：164(M+H)
+.
(2), 3,4-dihydroxyl methyl-butyrate synthetic
(2g 12.3mmol) is dissolved in the methyl alcohol L MALIC ACID dimethyl ester of step (1) gained, 0 ℃, slowly adds KBH
4(0.73g 13.6mmol), then, adds BiBr
3(2.0g 4.5mmol), stirred 2 hours, filtered, and concentrated, column chromatography get yellow liquid 1.1g, productive rate 67%.
[α]
D 25＝-3.0(c?0.66，CH
3OH)；
1H?NMR(CDCl
3，300MHz)：2.55(2H，m)，3.51(1H，m)，3.67(1H，m)，3.71(3H，s)，4.12(1H，m)ppm；
MS(EI，m/z)：135(M+H)
+.
(3), S-hydroxyl-gamma-butyrolactone is synthetic
With 3 of step (2) gained, (147mg 1.1mmol) is dissolved in the tetrahydrofuran (THF) 4-dihydroxyl methyl-butyrate, adds the 10%H of 15mL
2SO
4Reflux 2 hours.Mixture is chilled to room temperature, in the impouring water, and extracted with diethyl ether 3 times (15ml * 3).Merge organic phase, organic phase saturated common salt water washing, anhydrous sodium sulfate drying spends the night, and filters, and concentrates, and column chromatography gets liquid 101mg, productive rate 90%.
[α]
D 25＝-86(c?2.5，C
2H
5OH)；
1H?NMR(300MHz，CDCl3)δ4.67(m，1H)，4.40(dd，J＝10.1，4.3Hz，1H)，4.29(dd，J＝10.1，0.8Hz，1H)，3.19(br，1H)，2.72(dd，J＝18.0，6.0Hz，1H)，2.50(dd，J＝18.0，0.8Hz，1H)；
MS(EI，m/z)：103(M+H)
+。
Embodiment 2
A kind of synthetic method of S-beta-hydroxy-gamma-butyrolactone comprises the steps:
(1), the L MALIC ACID dimethyl ester is synthetic
Under 0 ℃, Acetyl Chloride 98Min. (5ml) slowly adds in the methyl alcohol (300ml).After dripping off, (26.8g 0.2mol), slowly rises to room temperature, stirs 12h to add L MALIC ACID.Concentrate methyl alcohol, resistates is dissolved in the 250ml acetoacetic ester, and organic phase is washed with saturated sodium bicarbonate, water and saturated nacl aqueous solution, and drying concentrates, and gets intermediate.Intermediate is dissolved among the 2mlTHF, 0 ℃ drip down tetrabutyl ammonium fluoride (1.0M, 0.5ml, 0.5mmol), mixture stirred 3 hours down for 0 ℃, the dilution of 15ml ether, organic phase water, saturated nacl aqueous solution washing, drying, concentrate, obtain colourless oil liquid 26.4g, productive rate 90%.
[α]
D 25＝-7.50(c?3.45，MeOH)；
1H?NMR(CDCl
3，300MHz)：2.85(2H，m)，3.72(3H，s)，3.82(3H，s)，4.53(2H，m)ppm；
MS(EI，m/z)：164(M+H)
+.
(2), 3,4-dihydroxyl methyl-butyrate synthetic
(20g 0.123mol) is dissolved in the methyl alcohol L MALIC ACID dimethyl ester of step (1) gained, 0 ℃, slowly adds NaBH
4(5.16g 0.136mol), then, adds BiBr
3(20.0g 0.045mol), stirred 2 hours, filtered, and concentrated, column chromatography get yellow liquid 11.0g, productive rate 67%.
[α]
D 25＝-3.0(c?0.66，CH
3OH)；
1H?NMR(CDCl
3，300MHz)：2.55(2H，m)，3.51(1H，m)，3.67(1H，m)，3.71(3H，s)，4.12(1H，m)ppm；
MS(EI，m/z)：135(M+H)
+.
(3), S-hydroxyl-gamma-butyrolactone is synthetic
With 3 of step (2) gained, (147mg 1.1mmol) is dissolved in the tetrahydrofuran (THF) 4-dihydroxyl methyl-butyrate, adds the 10%H of 10mL
2SO
4Reflux 2 hours.Mixture is chilled to room temperature, in the impouring water, and extracted with diethyl ether 3 times (15ml * 3).Merge organic phase, organic phase saturated common salt water washing, anhydrous sodium sulfate drying spends the night, and filters, and concentrates, and column chromatography gets liquid 94mg, productive rate 84%.
[α]
D 25＝-86(c?2.5，C
2H
5OH)；
1H?NMR(300MHz，CDCl3)δ4.67(m，1H)，4.40(dd，J＝10.1，4.3Hz，1H)，4.29(dd，J＝10.1，0.8Hz，1H)，3.19(br，1H)，2.72(dd，J＝18.0，6.0Hz，1H)，2.50(dd，J＝18.0，0.8Hz，1H)；
MS(EI，m/z)：103(M+H)
+。
Embodiment 3
A kind of synthetic method of S-beta-hydroxy-gamma-butyrolactone comprises the steps:
(1), the L MALIC ACID dimethyl ester is synthetic
Under 0 ℃, Acetyl Chloride 98Min. (10ml) slowly adds in the methyl alcohol (500ml).After dripping off, (26.8g 0.2mol), slowly rises to room temperature, stirs 12h to add L MALIC ACID.Concentrate methyl alcohol, resistates is dissolved in the 250ml acetoacetic ester, and organic phase is washed with saturated sodium bicarbonate, water and saturated nacl aqueous solution, and drying concentrates, and gets intermediate.Intermediate is dissolved among the 5mlTHF, 0 ℃ drip down tetrabutyl ammonium fluoride (1.0M, 1.0ml, 1.0mmol), mixture stirred 3 hours down for 0 ℃, the dilution of 15ml ether, organic phase water, saturated nacl aqueous solution washing, drying, concentrate, obtain colourless oil liquid 26.7g, productive rate 91%.
[α]
D 25＝-7.50(c?3.45，MeOH)；
1H?NMR(CDCl
3，300MHz)：2.85(2H，m)，3.72(3H，s)，3.82(3H，s)，4.53(2H，m)ppm；
MS(EI，m/z)：164(M+H)
+.
(2), 3,4-dihydroxyl methyl-butyrate synthetic
(20g 0.123mol) is dissolved in the methyl alcohol L MALIC ACID dimethyl ester of step (1) gained, 0 ℃, slowly adds NaBH
4(3.42g 0.090mol), then, adds BiBr
3(20.0g 0.045mol), stirred 2 hours, filtered, and concentrated, column chromatography get yellow liquid 10.3g, productive rate 63%.
[α]
D 25＝-3.0(c?0.66，CH
3OH)；
1H?NMR(CDCl
3，300MHz)：2.55(2H，m)，3.51(1H，m)，3.67(1H，m)，3.71(3H，s)，4.12(1H，m)ppm；
MS(EI，m/z)：135(M+H)
+.
(3), S-hydroxyl-gamma-butyrolactone is synthetic
With 3 of step (2) gained, (134mg 1.0mmol) is dissolved in the tetrahydrofuran (THF) 4-dihydroxyl methyl-butyrate, adds the 10%H of 10mL
2SO
4Reflux 2 hours.Mixture is chilled to room temperature, in the impouring water, and extracted with diethyl ether 3 times (15ml * 3).Merge organic phase, organic phase saturated common salt water washing, anhydrous sodium sulfate drying spends the night, and filters, and concentrates, and column chromatography gets liquid 92mg, productive rate 82%.
[α]
D 25＝-86(c?2.5，C
2H
5OH)；
1H?NMR(300MHz，CDCl3)δ4.67(m，1H)，4.40(dd，J＝10.1，4.3Hz，1H)，4.29(dd，J＝10.1，0.8Hz，1H)，3.19(br，1H)，2.72(dd，J＝18.0，6.0Hz，1H)，2.50(dd，J＝18.0，0.8Hz，1H)；
MS(EI，m/z)：103(M+H)
+。
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (5)
1. the synthetic method of a S-beta-hydroxy-gamma-butyrolactone is characterized in that comprising the steps:
(1), the L MALIC ACID dimethyl ester is synthetic
Methyl alcohol and Acetyl Chloride 98Min. add the solid L MALIC ACID after mixing under 0 ℃, rising to room temperature to solid dissolves, and reacts 12h again, concentrate methyl alcohol, resistates is dissolved in the ethyl acetate, and organic phase is washed with saturated sodium bicarbonate, water and saturated nacl aqueous solution, drying concentrates, and gets the product intermediate;
The gained intermediate is dissolved among the THF again, adds tetrabutyl ammonium fluoride again under 0 ℃, the mixture of gained stirred 3 hours down in 0 ℃, the ether dilution, organic phase water, saturated nacl aqueous solution washing, drying concentrates, colourless oil liquid L MALIC ACID dimethyl ester;
The proportioning of above-mentioned methyl alcohol, Acetyl Chloride 98Min. and solid L MALIC ACID, i.e. methyl alcohol: Acetyl Chloride 98Min.: the solid L MALIC ACID is 200ml～500ml: 5ml～10ml: 0.2mol;
Wherein the consumption of THF and tetrabutyl ammonium fluoride is pressed L MALIC ACID calculating, i.e. THF: tetrabutyl ammonium fluoride: L MALIC ACID is 2ml～5ml: 0.5mmol～1.0mmol: 0.2mol;
(2), 3,4-dihydroxyl methyl-butyrate synthetic
With the L MALIC ACID dimethyl ester of step (1) gained by BiBr
3, reaction generates 3 in the reduction system formed of hydroborate, lower alcohol, 4-dihydroxyl methyl-butyrate, reaction finishes the back removes solid filtering earlier, concentrate then 3,4-dihydroxyl methyl-butyrate;
Described lower alcohol is methyl alcohol, ethanol, propyl alcohol, Virahol or the trimethyl carbinol;
Described hydroborate is POTASSIUM BOROHYDRIDE or sodium borohydride;
Wherein by BiBr
3, BiBr in the reduction system formed of hydroborate, lower alcohol
3, hydroborate and lower alcohol mol ratio be 1: 2～5: 2～5, be preferably 1: 3: 3;
Wherein the L MALIC ACID dimethyl ester of step (1) gained with by BiBr
3, the reduction system formed of hydroborate, lower alcohol the quality proportioning, i.e. L MALIC ACID dimethyl ester: by BiBr
3, the reduction system formed of hydroborate, lower alcohol is 1: 2～5; Be preferably 1: 2;
(3), S-hydroxyl-gamma-butyrolactone is synthetic
With step (2) gained 3,4-dihydroxyl methyl-butyrate is under the catalysis of mineral acid, and control reaction temperature is 60 ℃, and the reaction times is 2 hours, i.e. cyclization generates S-hydroxyl-gamma-butyrolactone;
Described mineral acid is hydrochloric acid, sulfuric acid or nitric acid;
Wherein step (2) gained 3, the quality proportioning of 4-dihydroxyl methyl-butyrate and mineral acid, and promptly step (2) gained 3,4-dihydroxyl methyl-butyrate: mineral acid is 1: 5～10.
2. the synthetic method of a kind of S-beta-hydroxy-gamma-butyrolactone as claimed in claim 1, the proportioning that it is characterized in that the methyl alcohol described in the step (1), Acetyl Chloride 98Min. and solid L MALIC ACID, i.e. methyl alcohol: Acetyl Chloride 98Min.: the solid L MALIC ACID is preferably 300ml: 10ml: 0.2mol; The consumption of described THF and tetrabutyl ammonium fluoride is pressed L MALIC ACID and calculated, i.e. THF: tetrabutyl ammonium fluoride: L MALIC ACID is preferably 2.5ml: 0.6mmol: 0.2mol.
3. the synthetic method of a kind of S-beta-hydroxy-gamma-butyrolactone as claimed in claim 1 or 2 is characterized in that the BiBr described in the step (2)
3, BiBr in the reduction system formed of hydroborate, lower alcohol
3, hydroborate and lower alcohol mol ratio be preferably 1: 3: 3;
Described L MALIC ACID dimethyl ester with by BiBr
3, the reduction system formed of hydroborate, lower alcohol the quality proportioning, i.e. L MALIC ACID dimethyl ester: by BiBr
3, the reduction system formed of hydroborate, lower alcohol is preferably 1: 2.
4. the synthetic method of a kind of S-beta-hydroxy-gamma-butyrolactone as claimed in claim 3 is characterized in that 3 described in the step (3), the quality proportioning of 4-dihydroxyl methyl-butyrate and mineral acid, and promptly 3,4-dihydroxyl methyl-butyrate: mineral acid is preferably 1: 10.
5. the synthetic method of a kind of S-beta-hydroxy-gamma-butyrolactone as claimed in claim 1 or 2, it is characterized in that 3 described in the step (3), the quality proportioning of 4-dihydroxyl methyl-butyrate and mineral acid, promptly 3,4-dihydroxyl methyl-butyrate: mineral acid is preferably 1: 10.
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Cited By (2)
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| CN106596739A (en) * | 2015-10-14 | 2017-04-26 | 爱普香料集团股份有限公司 | Analysis method during chiral butyrolactone preparation |
| CN112939901A (en) * | 2021-02-09 | 2021-06-11 | 中国科学院福建物质结构研究所 | Preparation method of alpha-hydroxy-gamma-butyrolactone |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106596739A (en) * | 2015-10-14 | 2017-04-26 | 爱普香料集团股份有限公司 | Analysis method during chiral butyrolactone preparation |
| CN106596739B (en) * | 2015-10-14 | 2019-03-15 | 爱普香料集团股份有限公司 | Analysis method in chiral fourth butyrolactone preparation |
| CN112939901A (en) * | 2021-02-09 | 2021-06-11 | 中国科学院福建物质结构研究所 | Preparation method of alpha-hydroxy-gamma-butyrolactone |
| CN112939901B (en) * | 2021-02-09 | 2023-05-09 | 中国科学院福建物质结构研究所 | Preparation method of alpha-hydroxy-gamma-butyrolactone |
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