CN102477019A - Novel method for producing S-3-hydroxytetrahydrofuran - Google Patents

Novel method for producing S-3-hydroxytetrahydrofuran Download PDF

Info

Publication number
CN102477019A
CN102477019A CN201010561845XA CN201010561845A CN102477019A CN 102477019 A CN102477019 A CN 102477019A CN 201010561845X A CN201010561845X A CN 201010561845XA CN 201010561845 A CN201010561845 A CN 201010561845A CN 102477019 A CN102477019 A CN 102477019A
Authority
CN
China
Prior art keywords
compound
chloro
following material
solvent
alkoxyl group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201010561845XA
Other languages
Chinese (zh)
Inventor
陆军
顾铭
肖本良
张燕飞
杨进
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou Chireach Biomedical Technology Co ltd
Original Assignee
Suzhou Chireach Biomedical Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou Chireach Biomedical Technology Co ltd filed Critical Suzhou Chireach Biomedical Technology Co ltd
Priority to CN201010561845XA priority Critical patent/CN102477019A/en
Publication of CN102477019A publication Critical patent/CN102477019A/en
Pending legal-status Critical Current

Links

Landscapes

  • Saccharide Compounds (AREA)

Abstract

The invention discloses a new preparation method of an important medicine and pesticide intermediate-S-3-hydroxytetrahydrofuran, which starts from raw material S-4-chloro-3-hydroxybutyric acid ethyl ester and obtains a target product through hydroxyl protection, reduction reaction, cyclization reaction and deprotection reaction; the synthesis method has the advantages of high optical purity of the target product, excellent yield, simple and convenient reaction operation, environment-friendly process and suitability for industrial production.

Description

The novel method of preparation S-3-hydroxyl tetrahydrofuran
Technical field
The present invention relates to medicament preparation, specially refer to a kind of important medicine, agricultural chemicals optical activity midbody--the novel preparation method of S-3-hydroxyl tetrahydrofuran.
Background technology
Chirality is the universals between universe; The Nucleotide, amino acid and the monose that wherein constitute the life basic substance all have the chirality characteristic; The biomacromolecule nucleic acid, protein and the carbohydrate that are made up of them all have the characteristic space structure; This configuration characteristic has been established the basis that life generates and evolves, and has also determined chiral material (optically active substance) in numerous areas such as medical science, pesticide science, Materials science, critical role to be arranged.At present, optical activity medicine, agricultural chemicals have become the megatrend that pharmacy industry and agricultural chemicals thereof already develop with its unique character, excellent curative effect, and synthetic single opticity medicine has become the important goal and the means of chiral drug, pesticide research.
(S)-the 3-hydroxyl tetrahydrofuran is an important optical activity midbody that is used for synthesizing anti-AIDS thing (I, II, III); Simultaneously it also be applied to agricultural chemicals synthetic in; On diphenyl ether herbicide (IV) structure, introduce (S)-3-hydroxyl tetrahydrofuran group; The weeding activity and the selectivity of such weedicide can have been improved significantly; Thus it is clear that (S)-and the 3-hydroxyl tetrahydrofuran has good economic worth, and this structural formula of compound is as follows:
Figure BSA00000362357100011
(S)-the 3-hydroxyl tetrahydrofuran
Anti-AIDS thing and pesticide structure formula are as follows:
Figure BSA00000362357100012
For (S)-3-hydroxyl tetrahydrofuran, the compound method of report mainly contains following two kinds at present:
1, with the L MALIC ACID be starting raw material, obtain S-1 through esterification, reduction, 2, the 4-trihydroxybutane, the latter adds the heat-flash cyclodehydration and obtains title product [J.Org.Chem.1983,48:2767-2769 under acidic conditions; Chemical research and application 2 009,21:1070-1072; CN101367780A; CN 1887880A]; Utilize L MALIC ACID to be starting raw material, although raw materials cost is lower, reduzate S-1,2,4-trihydroxybutane purification difficulty is big, and is extremely difficult; In high temperature dehydration cyclization subsequently, by product is more, and productive rate is not ideal enough; In whole process of preparation, also exist aftertreatment numerous and diverse, use weak points such as quantity of solvent is too much, unfavorable to suitability for industrialized production.Its reaction formula is following:
Figure BSA00000362357100022
2, be raw material with S-4-chloro-ethyl 3-hydroxybutanoate, through reduction, the dehydrochlorination cyclisation obtains title product [US 6359155 under the acidic conditions; Use chemical industry 2008,37:191-193]; Realized under the prerequisite of suitability for industrialized production that at present S-4-chloro-ethyl 3-hydroxybutanoate it is short that this method has synthetic route, advantage easy and simple to handle; But intermediate product and the finished product are water-soluble very big, and product is difficult to from aqueous phase system, come together, and can cause using quantity of solvent many, and the not high shortcoming of productive rate is unfavorable for realizing suitability for industrialized production.Its reaction formula is following:
Figure BSA00000362357100031
In view of (S)-the 3-hydroxyl tetrahydrofuran has good pharmacy value and market outlook, seeks a kind of convenience and the compound method that is easy to control cost realizes that (S)-3-hydroxyl tetrahydrofuran suitability for industrialized production is very significant.
Summary of the invention
For addressing the above problem, the objective of the invention is to overcome above-mentioned deficiency, provide a kind of easy and simple to handle, cost is lower, and yield is higher, pollutes lessly, is suitable for the preparation method of (S)-3-hydroxyl tetrahydrofuran of suitability for industrialized production.
For achieving the above object, technical scheme of the present invention is: a kind of novel method of the S-3-of preparation hydroxyl tetrahydrofuran, it is characterized in that, and may further comprise the steps:
Step 1; With S-4-chloro-ethyl 3-hydroxybutanoate (compound two) is starting raw material; In suitable temperature, and under the effect of alkylating reagent, solvent and catalyzer, prepare S-4-chloro-3-alkoxyl group ethyl n-butyrate (compound three); R in the said S-4-chloro-3-alkoxyl group ethyl n-butyrate is carbonatoms at the alkyl of 1-8 and contains the aromatic base of different substituents group, said compound three as shown in the formula:
Step 2 is a raw material with the compound three that obtains in the step 1, in suitable temperature and molten
Under the agent condition; Utilize metal borohydride for going back original reagent; Prepare optically active S-4-chloro-3-alkoxyl group-1-butanols (compound four); R in said S-4-chloro-3-alkoxyl group-1-butanols is carbonatoms at the alkyl of 1-8 and contains the aromatic base of different substituents group), said compound four as shown in the formula:
Figure BSA00000362357100033
Step 3; Compound four to obtain in the step 2 is a raw material; Under suitable reagent, temperature and solvent condition; Prepare optically active S-3-alkoxyl group THF (compound five), the R in said optically active S-3-alkoxyl group THF is carbonatoms at the alkyl of 1-8 and contains the aromatic base of different substituents group, said compound five as shown in the formula:
Figure BSA00000362357100041
Step 4 is a raw material with the compound five that obtains in the step 3, under suitable alkylation removal condition, prepares target compound S-3-hydroxyl tetrahydrofuran (compound one), said compound one as shown in the formula:
Figure BSA00000362357100042
Preferably, the alkylating reagent described in the step 1 is at least a in the following material: methyl iodide, methyl-sulfate, Benzyl Chloride, to methoxybenzyl chloride, the trimethyl carbinol, iso-butylene; Solvent is one or more in the following material: ETHYLE ACETATE, methylene dichloride, benzene, toluene, THF, DMF, DMSO; Employed catalyzer is at least a in the following material: yellow soda ash, salt of wormwood, sodium hydroxide, Pottasium Hydroxide, pyridine, triethylamine, DMAP, sulfuric acid, hydrochloric acid, phosphoric acid, boron trifluoride-ether.
Preferably, employed metal borohydride is a kind of in Peng Qinghuana, the POTASSIUM BOROHYDRIDE 97MIN in the step 2; Employed catalyzer is at least a in the following material: zinc chloride, aluminum chloride, lithium chloride, iodine, the vitriol oil, ammonium sulfate, trimethylchlorosilane, calcium chloride, NSC 51149.
Preferably, the TR described in the step 3 is at 0-50 ℃; Described alkali is at least a in the following material: sodium hydroxide, Pottasium Hydroxide, sodium hydride, yellow soda ash, salt of wormwood, Quilonum Retard, triethylamine, pyridine, DMAP; The solvent that is adopted is at least a in the following material: toluene, YLENE, methyl alcohol, ethanol, methylene dichloride, THF, DMF, DMSO.
Preferably, the TR described in the step 4 is at 20-180 ℃; Said solvent is at least a in the following material: toluene, YLENE, methyl alcohol, ethanol, DMF, DMSO; The said alkoxyl group reagent that takes off is at least a in the following material: hydroiodic acid HI, Hydrogen bromide, boron trichloride, boron tribromide, aluminum chloride, boron trifluoride ethyl ether complex, sulfur alcohol sodium, lithium chloride, hydrogenchloride, hydrogen, trifluoroacetic acid.
Adopt the beneficial effect of present technique scheme to be: among the present invention hydroxyl is protected, it is fat-soluble to have increased midbody product, helps product and separates; Simultaneously, hydroxyl has been implemented protection, can reduce in the reaction process racemization phenomenon that product occurs significantly.Therefore, the title product optical purity of producing among the present invention is high, and easy and simple to handle, cost is lower, and yield is high, pollutes lessly, is suitable for suitability for industrialized production.
Embodiment
With regard to embodiment the present invention is done further detailed explanation below.
Embodiment 1,
Step 1, the preparation of S-4-chloro-3-methoxyl group ethyl n-butyrate.
100 gram S-4-chloro-ethyl 3-hydroxybutanoates are dissolved in 500 milliliters of toluene, and the frozen water cooling adds 190 gram yellow soda ash, under the vigorous stirring, slowly drip 91 gram methyl-sulfates; Dropwise, progressively rise to room temperature, after GC detection raw material reaction finishes, solids removed by filtration, organic layer washs with salt solution, and anhydrous sodium sulfate drying, pressure reducing and steaming solvent obtain 93.4 gram S-4-chloro-3-methoxyl group ethyl n-butyrates, yield 86%.
Step 2, the preparation of S-4-chloro-3-methoxyl group-1-butanols.
90 gram S-4-chloro-3-methoxyl group ethyl n-butyrates are dissolved in 150 milliliters of ethanol, and the frozen water cooling adds 23 gram Peng Qinghuanas, under the vigorous stirring, slowly drips 66 gram calcium chloride; Progressively rise to room temperature, after GC detection raw material reaction finishes, add 100 milliliter of 30% sodium hydroxide solution; Stirred 2 hours, and filtered, filtrating is used dichloromethane extraction; Organic layer is used anhydrous sodium sulfate drying, and the pressure reducing and steaming solvent obtains 58.2 gram S-4-chloro-3-methoxyl group-1-butanols, yield 84%.
Step 3, the preparation of S-3-methoxyl group THF.
100 gram S-4-chloro-3-methoxyl group-1-butanols are dissolved in 500 milliliters of toluene, under the vigorous stirring, slowly drip the methanol solution of 28.9 gram sodium hydroxide; 0 ℃ of stirring of temperature control, after GC detection raw material reaction finishes, the saturated common salt water washing, organic layer is used anhydrous sodium sulfate drying, the pressure reducing and steaming solvent, underpressure distillation obtains 50 gram S-3-methoxyl group THFs, yield 68%.
The preparation of step 4 S-3-hydroxyl tetrahydrofuran.
(a), 60 gram S-3-methoxyl group THFs are dissolved in 100 milliliters of dry DMF, add 55 gram sulfur alcohol sodium, in 150 ℃ of reactions 15 hours; Cooling, reaction solution is poured in the water, after fully stirring; Ethyl acetate extraction, organic layer is used anhydrous sodium sulfate drying, behind the pressure reducing and steaming solvent; Underpressure distillation obtains 23.3 gram S-3-hydroxyl tetrahydrofurans, yield 45%; Purity＞98% (GC), 1H NMR (400MHz, CDCl3): δ 4.51-4.49 (m, 1H), 4.02-3.94 (m, 1H), 3.89-3.79 (m, 1H), 3.78-3.72 (m, 2H), 2.53 (br s, 1H), 2.14-2.02 (m, 1H), 1.95-1.80 (m, 1H); 13CNMR (100MHz, CDCl3): δ 75.3,71.6, and 66.5,35.2.
(b), 60 gram S-3-methoxyl group THFs are dissolved in 100 milliliters of dry DMF, add 55 gram sulfur alcohol sodium, in 180 ℃ of reactions 10 hours; Cooling, reaction solution is poured in the water, after fully stirring; Ethyl acetate extraction, organic layer is used anhydrous sodium sulfate drying, behind the pressure reducing and steaming solvent; Underpressure distillation obtains 18.6 gram S-3-hydroxyl tetrahydrofurans, yield 36%; Purity＞98% (GC).
Embodiment 2:
The preparation of step 1:S-4-chloro-3-tert.-butoxy ethyl n-butyrate:
100 gram S-4-chloro-ethyl 3-hydroxybutanoates are dissolved in 400 milliliters of methylene dichloride, add 2 milliliters of vitriol oils, are cooled to-20 ℃, under the vigorous stirring, slowly feed iso-butylene to volume and double; Progressively rise to room temperature, after GC detection raw material reaction finishes, after the frozen water washing, the sodium carbonate solution washing, organic layer is used anhydrous sodium sulfate drying, and the pressure reducing and steaming solvent obtains 131 gram S-4-chloro-3-tert.-butoxy ethyl n-butyrates, yield 98%.
The preparation of step 2:S-4-chloro-3-tert.-butoxy-1-butanols:
18.8 the gram Peng Qinghuana is suspended in 200 milliliters of THFs, 40 ℃ of temperature controls slowly drip the tetrahydrofuran solution of 100 gram S-4-chloro-3-tert.-butoxy ethyl n-butyrates; Dropwise, in 40 ℃ react completely (GC detections), removal of solvent under reduced pressure; With the 4N hcl acidifying to pH value 2-3, ethyl acetate extraction, organic layer is used anhydrous sodium sulfate drying; The pressure reducing and steaming solvent obtains 78 gram S-4-chloro-3-tert.-butoxy-1-butanols, yield 96%.
The preparation of step 3:S-3-tert.-butoxy THF:
100 gram S-4-chloro-3-tert.-butoxy-1-butanols are dissolved in 500 ml methanol, add 153 gram salt of wormwood, 50 ℃ of vigorous stirring of temperature control; After GC detection raw material reaction finishes, filter, removal of solvent under reduced pressure, behind acetic acid ethyl dissolution, washing, organic layer is used anhydrous sodium sulfate drying, and the pressure reducing and steaming solvent obtains 73.3 gram S-3-tert.-butoxy THFs, yield 92%.
The preparation of step 4:S-3-hydroxyl tetrahydrofuran:
100 gram S-3-tert.-butoxy THFs are dissolved in 300 milliliters of anhydrous methanols, and the frozen water cooling feeds hydrogen chloride gas; Progressively rise to 20 ℃, continue to stir 20 hours (GC detects, and reacts completely); Behind the pressure reducing and steaming solvent, underpressure distillation obtains 60 gram S-3-methoxyl group THFs, yield 98%; Purity＞98% (GC),
1H?NMR(400MHz，CDCl3)：
4.51-4.49(m，1H)，4.02-3.94(m，1H)，3.89-3.79(m，1H)，3.78-3.72(m，2H)，2.53(br?s，1H)，2.14-2.02(m，1H)，1.95-1.80(m，1H)；13C?NMR(100MHz，CDC?13)：75.3，71.6，66.5，35.2。
Embodiment 3:
The preparation of step 1:S-4-chloro-3-benzyloxy ethyl n-butyrate
100 gram S-4-chloro-ethyl 3-hydroxybutanoates are dissolved in 500 milliliters of THFs, and the frozen water cooling adds 127 gram yellow soda ash, under the vigorous stirring, slowly drip 83.6 gram Benzyl Chlorides; Dropwise, progressively rise to room temperature, after GC detection raw material disappears and finishes, solids removed by filtration, organic layer washs with salt solution, and anhydrous sodium sulfate drying, pressure reducing and steaming solvent obtain 120 gram S-4-chloro-3-benzyloxy ethyl n-butyrates, yield 78%.
The preparation of step 2:S-4-chloro-3-benzyloxy-1-butanols
Under the nitrogen protection; 19 gram Peng Qinghuanas and 21 grams lithium chlorides are suspended in 100 milliliters of THFs, and high degree of agitation ten minutes is with 500 milliliters of ethanolic solns of 128 gram S-4-chloro-3-benzyloxy ethyl n-butyrates; Under ice bath, slowly splash into, dropwise continuation stirring at room 24 hours; After GC detects raw material reaction and finishes, removal of solvent under reduced pressure, with the 4N hcl acidifying to pH value 2-3, ethyl acetate extraction, organic layer is used anhydrous sodium sulfate drying, the pressure reducing and steaming solvent obtains 102 and restrains S-4-chloro-3-benzyloxy-1-butanols, yield 95%.
The preparation of step 3:S-3-benzyloxy THF
100 gram S-4-chloro-3-benzyloxy-1-butanols are dissolved in 500 milliliters of methylene dichloride; Add 38 gram Quilonum Retards; 25 ℃ of vigorous stirring of temperature control are to react completely (GC detection), the saturated common salt water washing, and organic layer is used anhydrous sodium sulfate drying; The pressure reducing and steaming solvent obtains 66.4 gram S-3-benzyloxy THFs, yield 80%.
The preparation of step 4:S-3-hydroxyl tetrahydrofuran:
100 gram S-3-benzyloxy THFs are dissolved in 400 ml methanol, add 2 gram palladium carbon catalysts, and room temperature feeds hydrogen reaction; After GC detection raw material reaction finishes, filter, behind the pressure reducing and steaming solvent; Underpressure distillation obtains 44.4 gram S-3-hydroxyl tetrahydrofurans, yield 90%; Purity＞98% (GC),
Figure BSA00000362357100081
1H?NMR(400MHz，CDC13)：
4.51-4.49(m，1H)，4.02-3.94(m，1H)，3.89-3.79(m，1H)，3.78-3.72(m，2H)，2.53(br?s，1H)，2.14-2.02(m，1H)，1.95-1.80(m，1H)；13C?NMR(100MHz，CDCl3)：75.3，71.6，66.5，35.2。
In the foregoing description, the TR described in the step 3 is at 0-50 ℃; TR described in the step 4 is at 20-180 ℃.
Adopt the beneficial effect of present technique scheme to be: among the present invention hydroxyl is protected, it is fat-soluble to have increased midbody product, helps product and separates; Simultaneously, hydroxyl has been implemented protection, can reduce in the reaction process racemization phenomenon that product occurs significantly.Therefore, the title product optical purity of producing among the present invention is high, and easy and simple to handle, cost is lower, and yield is high, pollutes lessly, is suitable for suitability for industrialized production.
Above-described only is preferred implementation of the present invention, should be pointed out that for the person of ordinary skill of the art, under the prerequisite that does not break away from the invention design, can also make some distortion and improvement, and these all belong to protection scope of the present invention.

Claims (5)

1. a novel method for preparing the S-3-hydroxyl tetrahydrofuran is characterized in that, may further comprise the steps:
Step 1; With S-4-chloro-ethyl 3-hydroxybutanoate (compound two) is starting raw material; In suitable temperature, and under the effect of alkylating reagent, solvent and catalyzer, prepare S-4-chloro-3-alkoxyl group ethyl n-butyrate (compound three); R in the said S-4-chloro-3-alkoxyl group ethyl n-butyrate is carbonatoms at the alkyl of 1-8 and contains the aromatic base of different substituents group, said compound three as shown in the formula:
Figure FSA00000362357000011
Step 2; Compound three to obtain in the step 1 is a raw material; Under suitable temperature and solvent condition, utilize metal borohydride for going back original reagent, prepare optically active S-4-chloro-3-alkoxyl group-1-butanols (compound four); R in said S-4-chloro-3-alkoxyl group-1-butanols is carbonatoms at the alkyl of 1-8 and contains the aromatic base of different substituents group), said compound four as shown in the formula:
Figure FSA00000362357000012
Step 3; Compound four to obtain in the step 2 is a raw material; Under suitable reagent, temperature and solvent condition; Prepare optically active S-3-alkoxyl group THF (compound five), the R in said optically active S-3-alkoxyl group THF is carbonatoms at the alkyl of 1-8 and contains the aromatic base of different substituents group, said compound five as shown in the formula:
Step 4 is a raw material with the compound five that obtains in the step 3, under suitable alkylation removal condition, prepares target compound S-3-hydroxyl tetrahydrofuran (compound one), said compound one as shown in the formula:
Figure FSA00000362357000021
2. the novel method of preparation S-3-hydroxyl tetrahydrofuran as claimed in claim 1; It is characterized in that the alkylating reagent described in the step 1 is at least a in the following material: methyl iodide, methyl-sulfate, Benzyl Chloride, to methoxybenzyl chloride, the trimethyl carbinol, iso-butylene; Solvent is one or more in the following material: ETHYLE ACETATE, methylene dichloride, benzene, toluene, THF, DMF, DMSO; Employed catalyzer is at least a in the following material: yellow soda ash, salt of wormwood, sodium hydroxide, Pottasium Hydroxide, pyridine, triethylamine, DMAP, sulfuric acid, hydrochloric acid, phosphoric acid, boron trifluoride-ether.
3. the novel method of preparation as claimed in claim 1 S-3-hydroxyl tetrahydrofuran is characterized in that, employed metal borohydride is a kind of in Peng Qinghuana, the POTASSIUM BOROHYDRIDE 97MIN in the step 2; Employed catalyzer is at least a in the following material: zinc chloride, aluminum chloride, lithium chloride, iodine, the vitriol oil, ammonium sulfate, trimethylchlorosilane, calcium chloride, NSC 51149.
4. the novel method of preparation S-3-hydroxyl tetrahydrofuran as claimed in claim 1 is characterized in that the TR described in the step 3 is at 0-50 ℃; Described alkali is at least a in the following material: sodium hydroxide, Pottasium Hydroxide, sodium hydride, yellow soda ash, salt of wormwood, Quilonum Retard, triethylamine, pyridine, DMAP; The solvent that is adopted is at least a in the following material: toluene, YLENE, methyl alcohol, ethanol, methylene dichloride, THF, DMF, DMSO.
5. the novel method of preparation S-3-hydroxyl tetrahydrofuran as claimed in claim 1 is characterized in that the TR described in the step 4 is at 20-180 ℃; Said solvent is at least a in the following material: toluene, YLENE, methyl alcohol, ethanol, DMF, DMSO; The said alkoxyl group reagent that takes off is at least a in the following material: hydroiodic acid HI, Hydrogen bromide, boron trichloride, boron tribromide, aluminum chloride, boron trifluoride ethyl ether complex, sulfur alcohol sodium, lithium chloride, hydrogenchloride, hydrogen, trifluoroacetic acid.
CN201010561845XA 2010-11-26 2010-11-26 Novel method for producing S-3-hydroxytetrahydrofuran Pending CN102477019A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201010561845XA CN102477019A (en) 2010-11-26 2010-11-26 Novel method for producing S-3-hydroxytetrahydrofuran

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201010561845XA CN102477019A (en) 2010-11-26 2010-11-26 Novel method for producing S-3-hydroxytetrahydrofuran

Publications (1)

Publication Number Publication Date
CN102477019A true CN102477019A (en) 2012-05-30

Family

ID=46089810

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201010561845XA Pending CN102477019A (en) 2010-11-26 2010-11-26 Novel method for producing S-3-hydroxytetrahydrofuran

Country Status (1)

Country Link
CN (1) CN102477019A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104961711A (en) * 2015-07-23 2015-10-07 沧州那瑞化学科技有限公司 Preparation method of (S)-3-hydroxytetrahydrofuran and (R)-3-hydroxytetrahydrofuran
CN105669608A (en) * 2016-02-29 2016-06-15 苏州艾缇克药物化学有限公司 Preparing method of (S)-3-hydroxy tetrahydrofuran
US10703719B2 (en) * 2013-12-27 2020-07-07 Api Corporation Method for producing 5-hydroxypiperidine-2-carboxylic acid
CN115611829A (en) * 2021-07-13 2023-01-17 中化医药有限公司 Preparation method of (S) -3-hydroxytetrahydrofuran

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0761663A1 (en) * 1995-09-08 1997-03-12 Takasago International Corporation Process for preparing optically active 3-hydroxy furan compounds
EP1088820A1 (en) * 1999-04-15 2001-04-04 Kaneka Corporation Process for the preparation of 3-hydroxytetrahydrofuran
CN1887880A (en) * 2006-07-20 2007-01-03 厦门大学 Synthesis of S-(3)-hydroxy tetrahydrofuran
WO2008093955A1 (en) * 2007-02-01 2008-08-07 Rstech Corporation Process for the efficient preparation of 3-hydroxytetrahydrofuran

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0761663A1 (en) * 1995-09-08 1997-03-12 Takasago International Corporation Process for preparing optically active 3-hydroxy furan compounds
EP1088820A1 (en) * 1999-04-15 2001-04-04 Kaneka Corporation Process for the preparation of 3-hydroxytetrahydrofuran
CN1887880A (en) * 2006-07-20 2007-01-03 厦门大学 Synthesis of S-(3)-hydroxy tetrahydrofuran
WO2008093955A1 (en) * 2007-02-01 2008-08-07 Rstech Corporation Process for the efficient preparation of 3-hydroxytetrahydrofuran

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YOSHIFUMI YUASA，等: "Practical syntheses of (S)-4-hydroxytetrahydrofuran-2-one, (S)-3-hydroxytetrahydrofuran, and their (R)-enantiomers", 《LIEBIGS ANNALEN/RECUEIL》, vol. 1997, no. 9, 27 January 2006 (2006-01-27) *
李勇智，等: "手性化合物(S)-3-羟基四氢呋喃的合成", 《应用化工》, vol. 37, no. 2, 29 February 2008 (2008-02-29) *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10703719B2 (en) * 2013-12-27 2020-07-07 Api Corporation Method for producing 5-hydroxypiperidine-2-carboxylic acid
CN111499562A (en) * 2013-12-27 2020-08-07 株式会社Api Method for producing 5-hydroxypiperidine-2-carboxylic acid
CN111499562B (en) * 2013-12-27 2023-12-26 株式会社Api Process for producing 5-hydroxypiperidine-2-carboxylic acid
CN104961711A (en) * 2015-07-23 2015-10-07 沧州那瑞化学科技有限公司 Preparation method of (S)-3-hydroxytetrahydrofuran and (R)-3-hydroxytetrahydrofuran
CN104961711B (en) * 2015-07-23 2017-03-08 沧州那瑞化学科技有限公司 （S）3 hydroxyl tetrahydrofurans and（R）The preparation method of 3 hydroxyl tetrahydrofurans
CN105669608A (en) * 2016-02-29 2016-06-15 苏州艾缇克药物化学有限公司 Preparing method of (S)-3-hydroxy tetrahydrofuran
CN115611829A (en) * 2021-07-13 2023-01-17 中化医药有限公司 Preparation method of (S) -3-hydroxytetrahydrofuran

Similar Documents

Publication Publication Date Title
CN102557977B (en) Synthesis intermediate of erlotinib and preparation method thereof
CN105541844B (en) Simple preparation method of high-purity linagliptin
CN102875537A (en) Novel preparation method of antithrombosis medicine
CN110790721B (en) Synthetic method of ceftazidime side chain ethyl ester
CN102180823B (en) A kind of method of refining prolinamide
CN102477019A (en) Novel method for producing S-3-hydroxytetrahydrofuran
CN102367260A (en) Synthesis method of 2-aminopyrimidine-5-boric acid
CN110452269B (en) Method for preparing tenofovir by using microreactor
CN106674084A (en) Preparation method of 2-isopropoxy-5-methyl-4-(piperidine-4-yl) aniline dihydrochloride
CN108530402B (en) Preparation method of (R) -3-propyl-gamma-butyrolactone
CN114805134B (en) Synthesis method of (1-hydroxypent-4-en-2-yl) carbamic acid tert-butyl ester
CN102633802B (en) Intermediate for synthesizing 2-chloro-7H-pyrrolo (2, 3-d) pyrimidine and preparation method thereof
CN107674016B (en) Preparation method of telaprevir intermediate and intermediate thereof
CN111302997B (en) Method for preparing Raatinib intermediate by one-pot method
CN104478799B (en) The preparation method of 1,4-diallylisoquinoline
CN101298448B (en) Synthetic method of 2-benzyloxy-3-ethyl-4-methyl-5-chloro-6-[(tetrahydro-2H-pyrrole-2-oxyl)methyl ] phenol
CN108314688A (en) A kind of synthetic method of sitagliptin
CN107382785A (en) One planting sand storehouse must bent key intermediate preparation method
CN114605437A (en) Synthesis process for preparing three telaprevir medicaments by continuous one-pot method
CN109265385B (en) Synthesis process of chiral catalyst
CN114702425A (en) Preparation method of (S) -2-amino- (S) -3- [ pyrrolidone-2' ] alanine derivative and intermediate
CN102675294A (en) Method of synthesizing losartan and losartan intermediates
CN109232282B (en) Synthetic method of 2-aminobenzophenone compound
CN106554301A (en) A kind of preparation method of BMS-477118 key intermediate
CN104610215A (en) Preparation method of nebivolol intermediates and preparation method of nebivolol

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20120530