CN107827748A - Synthesis method of 2-allyl cyclopropyl acetate racemate - Google Patents
Synthesis method of 2-allyl cyclopropyl acetate racemate Download PDFInfo
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- CN107827748A CN107827748A CN201711126406.4A CN201711126406A CN107827748A CN 107827748 A CN107827748 A CN 107827748A CN 201711126406 A CN201711126406 A CN 201711126406A CN 107827748 A CN107827748 A CN 107827748A
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- China
- Prior art keywords
- acetic acid
- propyl ester
- ring propyl
- epoxide
- raceme
- Prior art date
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Links
- 238000001308 synthesis method Methods 0.000 title abstract 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 183
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 55
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical compound C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 claims abstract description 51
- -1 2- (3- ((tert-butyldimethylsilyl) oxy) propyl) cyclopropyl Chemical group 0.000 claims abstract description 11
- 238000003379 elimination reaction Methods 0.000 claims abstract description 3
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 109
- 150000002118 epoxides Chemical class 0.000 claims description 57
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 50
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 23
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- 238000010189 synthetic method Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- YSHOWEKUVWPFNR-UHFFFAOYSA-N burgess reagent Chemical compound CC[N+](CC)(CC)S(=O)(=O)N=C([O-])OC YSHOWEKUVWPFNR-UHFFFAOYSA-N 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 7
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 235000002639 sodium chloride Nutrition 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 230000021736 acetylation Effects 0.000 claims description 2
- 238000006640 acetylation reaction Methods 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 150000001263 acyl chlorides Chemical class 0.000 claims 1
- HHSARRMUXPDGJD-UHFFFAOYSA-N butyl(dimethyl)silicon Chemical compound CCCC[Si](C)C HHSARRMUXPDGJD-UHFFFAOYSA-N 0.000 claims 1
- 238000003682 fluorination reaction Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000000397 acetylating effect Effects 0.000 abstract 1
- OZYHLCOUAISLLG-UHFFFAOYSA-N cyclopropyl acetate Chemical class CC(=O)OC1CC1 OZYHLCOUAISLLG-UHFFFAOYSA-N 0.000 abstract 1
- 238000001819 mass spectrum Methods 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 230000006340 racemization Effects 0.000 description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- JHTJPSCVBLCXEO-UHFFFAOYSA-N n-(triethylazaniumyl)sulfonylcarbamate Chemical compound CC[N+](CC)(CC)S(=O)(=O)NC([O-])=O JHTJPSCVBLCXEO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MZBLZLWXUBZHSL-FZNJKFJKSA-N O=C([C@H]1N2C[C@H](OC3=NC4=CC(OC)=CC=C4N=C3C(F)(F)CCCC[C@@H]3C[C@H]3OC(=O)N[C@H](C2=O)C(C)(C)C)[C@H]1CC)N[C@]1(C(=O)NS(=O)(=O)C2(C)CC2)C[C@H]1C(F)F Chemical compound O=C([C@H]1N2C[C@H](OC3=NC4=CC(OC)=CC=C4N=C3C(F)(F)CCCC[C@@H]3C[C@H]3OC(=O)N[C@H](C2=O)C(C)(C)C)[C@H]1CC)N[C@]1(C(=O)NS(=O)(=O)C2(C)CC2)C[C@H]1C(F)F MZBLZLWXUBZHSL-FZNJKFJKSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 238000006129 Kulinkovich cyclopropane synthesis reaction Methods 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- PPLBEZQBVNEXGC-UHFFFAOYSA-L [CH3].I[Zn]I Chemical compound [CH3].I[Zn]I PPLBEZQBVNEXGC-UHFFFAOYSA-L 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 208000006454 hepatitis Diseases 0.000 description 1
- 231100000283 hepatitis Toxicity 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- VURPSIJHXNVCNZ-UHFFFAOYSA-N isocyanic acid;urea Chemical compound N=C=O.NC(N)=O VURPSIJHXNVCNZ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- LKPFBGKZCCBZDK-UHFFFAOYSA-N n-hydroxypiperidine Chemical compound ON1CCCCC1 LKPFBGKZCCBZDK-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229950004638 voxilaprevir Drugs 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/297—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of 2-allyl cyclopropyl acetate racemate, which comprises the following steps: (1) acetylating the 2- (3- ((tert-butyldimethylsilyl) oxy) propyl) cyclopropyl alcohol racemate to obtain the acetic acid 2- (3- ((tert-butyldimethylsilyl) oxy) propyl) cyclopropyl ester racemate; (2) protecting the 2- (3- ((tert-butyl dimethyl silicon) oxy) propyl) cyclopropyl acetate racemate by desiliconization to obtain the 2- (3-hydroxypropyl) cyclopropyl acetate racemate; (3) the 2- (3-hydroxypropyl) cyclopropyl acetate racemate undergoes elimination reaction to obtain the 2-allyl cyclopropyl acetate racemate. The invention has the advantages that: provides a brand new synthesis method of 2-allyl cyclopropyl acetate racemate, and the synthesis raw material of pentanediol is low in price and easy to obtain, and the total yield of the synthesis route is high.
Description
Technical field
The present invention relates to organic synthesis technical field, is more particularly to a kind of acetic acid 2- allyls basic ring propyl ester raceme
Synthetic method.
Background technology
Acetic acid 2- allyl basic ring propyl ester racemies are the key intermediates for synthesizing hepatitis medicine Fu Xiruiwei.Fu Xirui
The molecular formula of Wei (voxilaprevir) is C40H52F4N6O9S, structure are shown below：
。
The structure of acetic acid 2- allyl basic ring propyl ester racemies is shown below：
Wherein, (1S, 2S)-acetic acid 2- allyl basic rings propyl ester (compound shown in Formulas I) and (1R, 2R)-acetic acid 2- allyls
The ratio of basic ring propyl ester (compound shown in Formula II) is 50:50.
Acetic acid 2- allyl basic ring propyl ester racemies can generally react (Kulinkovich Reaction) through Ku Linkeweiqi
Obtain, but the bromo- 1- amylenes of its raw material 5- are expensive, and reaction yield is low, and specific synthetic route is as follows：
Therefore, finding a kind of synthetic method of low, high income the acetic acid 2- allyls basic ring propyl ester raceme of production cost is
It is badly in need of the technical problem solved at present.
The content of the invention
The technical problems to be solved by the invention are the provision of that a kind of cost is cheap, acetic acid 2- allyl basic rings of high income
The synthetic method of propyl ester raceme.
The present invention is that solve above-mentioned technical problem by the following technical programs：
A kind of synthetic method of acetic acid 2- allyls basic ring propyl ester raceme, comprises the following steps：
(1) (1S, 2S) -2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl alcohol and (1R, 2R) -2- (3-
((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl alcohol raceme through acetylation, obtains (1S, 2S)-acetic acid 2- (3- ((tertiary fourths
Base dimethyl silicon substrate) epoxide) propyl group) ring propyl ester and (1R, 2R)-acetic acid 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group)
Ring propyl ester raceme；
(2) (1S, 2S)-acetic acid 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester and (1R, 2R)-acetic acid
2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester raceme obtains (1S, 2S)-acetic acid 2- through de- protected silane
(3- hydroxypropyls) ring propyl ester and (1R, 2R)-acetic acid 2- (3- hydroxypropyls) ring propyl ester raceme；
(3) (1S, 2S)-acetic acid 2- (3- hydroxypropyls) ring propyl ester and (1R, 2R)-acetic acid 2- (3- hydroxypropyls) ring propyl ester racemization
Body obtains (1S, 2S)-acetic acid 2- allyl basic ring propyl ester and the 2- allyl basic ring propyl ester racemizations of (1R, 2R)-acetic acid through elimination reaction
Body.
Preferably, the synthetic method comprises the following steps：
(1) by (1S, 2S) -2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl alcohol and (1R, 2R) -2- (3-
((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl alcohol raceme, methyl tertiary butyl ether(MTBE) and triethylamine be cooled to 0~10 DEG C plus
Enter chloroacetic chloride, be stirred overnight after being warming up to 20~30 DEG C, aqueous hydrochloric acid solution is added dropwise, washing organic phase, is concentrated under reduced pressure into dry, acquisition
(1S, 2S)-acetic acid 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester and (1R, 2R)-acetic acid 2- (3- ((tertiary fourths
Base dimethyl silicon substrate) epoxide) propyl group) ring propyl ester raceme；
(2) by (1S, 2S)-acetic acid 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester and (1R, 2R)-second
Sour 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester raceme is dissolved in tetrahydrofuran, adds tetra-n-butyl
The tetrahydrofuran solution of ammonium fluoride, 20~30 DEG C stirring 1~3h, through dilute, wash, be concentrated under reduced pressure into it is dry, obtain (1S, 2S)-
Acetic acid 2- (3- hydroxypropyls) ring propyl ester and (1R, 2R)-acetic acid 2- (3- hydroxypropyls) ring propyl ester raceme；
(3) (1S, 2S)-acetic acid 2- (3- hydroxypropyls) ring propyl ester and (1R, 2R)-acetic acid 2- (3- hydroxypropyls) ring propyl ester are disappeared
Rotation body is dissolved in glycol dimethyl ether, adds burgess reagent, is heated to 40~60 DEG C of reaction 0.5-2h, drop under nitrogen protection
Temperature to 20~30 DEG C, add methyl tertiary butyl ether(MTBE), it is scrubbed, drys, be concentrated under reduced pressure into it is dry, acquisition (1S, 2S)-acetic acid 2- allyls
Basic ring propyl ester and (1R, 2R)-acetic acid 2- allyl basic ring propyl ester racemies.
Preferably, in step (1), (1S, 2S) -2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl alcohol and
(1R, 2R) -2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl alcohol raceme：Triethylamine：The mass ratio of chloroacetic chloride
For 1~2:1~3:1.
Preferably, in step (1), the process of the washing is successively with saturated sodium bicarbonate and saturated common salt washing
Wash.More electedly, the volume ratio of the saturated sodium bicarbonate and saturated aqueous common salt is 1:1.
Preferably, in step (2), per 1g (1S, 2S)-acetic acid 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group)
Add 6 in ring propyl ester and (1R, 2R)-acetic acid 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester raceme~
The tetrahydrofuran solution of 9mL tetra-n-butyl ammonium fluorides.
Preferably, in step (2), the reagent of the dilution is ethyl acetate；And/or
The process of the washing is first to be washed with aqueous hydrochloric acid solution, then is eaten successively with saturated sodium bicarbonate aqueous solution and saturation
Salt water washing.It is highly preferred that aqueous hydrochloric acid solution：Saturated sodium bicarbonate aqueous solution：The volume ratio of saturated aqueous common salt is 1.5:1:1,
The concentration of the aqueous hydrochloric acid solution is 1mol/L.
Preferably, in step (3), (1S, 2S)-acetic acid 2- (3- hydroxypropyls) ring propyl ester and (1R, 2R)-acetic acid 2- (3-
Hydroxypropyl) ring propyl ester raceme：The mass ratio of burgess reagent is 1:1~3.
Preferably, in step (3), the reagent of the washing is saturated aqueous common salt；And/or
It is described dry that reagent is anhydrous sodium sulfate.
The acetic acid 2- allyl basic ring propyl ester racemies that synthetic method of the present invention obtains are in Fu Xiruiwei is prepared
Purposes.
The present invention has advantages below compared with prior art：A kind of brand-new acetic acid 2- allyl basic ring propyl ester racemies are provided
Synthetic method, and synthesis material pentanediol is cheap and easy to get, and synthetic route total recovery is high；In addition, participated in using TBAF normal
Warm desiliconization alkane protective condition, prevent from removing acetyl group or migrate acetyl group, and gentle disappear is carried out using Burgess reagents
Except reaction, the success to this route is most important.
Brief description of the drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the acetic acid 2- allyl basic ring propyl ester racemies of the present invention.
Embodiment
Embodiments of the invention are elaborated below, the present embodiment is carried out lower premised on technical solution of the present invention
Implement, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation
Example.
All chemicals are commercial chemicals.
In following preparation examples,1H-NMR Varian Mercury AMX300 types instrument, Varian Mercury-300
High Performance Digital FT-NMR types instrument, the NMR types instrument of Bruker Ultrashield 500, Varian
Mercury-400 High Performance Digital FT-NMR types instrument, the Prospekt 2 of Agilent 1260
The NMR types instrument of Bruker Ascend 600 determines, deuterochloroform (CDCl3), deuterated methanol (MeOD-d4) it is solvent, tetramethylsilane
Alkane (TMS) is internal standard.Mass spectrum Thermo Finnigan MAT-95 types instrument, Waters Q-Tof Ultima Global
Spectrometer types instrument determines.Fusing point determines on SGW X-4 melting point apparatus.
(1S, 2S) -2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl alcohol and formula shown in the Formula IV of embodiment 1
The preparation of (1R, 2R) -2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl alcohol raceme shown in VII
Synthetic route is as follows：
1,5-PD (5.2g, 50mmol) and imidazoles (0.34g, 5mmol) are added in there-necked flask, nitrogen displacement 3 times, is added
Enter dichloromethane (250mL), 0 DEG C is cooled under stirring, tert-butyl chloro-silicane (12.3g, 55mmol) is added dropwise, then be added dropwise
Triethylamine (6.1g, 60mmol).Reaction solution is warming up to room temperature, the lower reaction of nitrogen protection 18 hours.Dropwise addition 200mL water, liquid separation,
Organic phase uses 200mL water successively, the washing of 200mL saturated sodium-chloride water solutions, is concentrated under reduced pressure into dry, obtains grease crude product
(9.8g), yield 90%.Above-mentioned grease crude product (9.0g, 41mmol) is added into pre- 2,2,6, the 6- tetramethyls for being cooled to 0 DEG C
In dichloromethane (200mL) solution of piperidine oxide (320mg, 2.1mmol), then be added portionwise trichlorine isocyanic acid urea (7.6g,
32.8mmol).Reaction solution is warming up to room temperature reaction 6 hours, adds normal heptane (200mL) dilute reaction solution, is stirred 1 hour,
Filtering, filtrate decompression are concentrated to dryness, are transferred to 50mL tetrahydrofurans in there-necked flask.Above-mentioned solution is cooled down under nitrogen protection
To 0 DEG C, methyl zinc diiodide (123mL, 0.5mol/L tetrahydrofuran solution) is added dropwise, is added dropwise within 0.5 hour, is stirred at 0 DEG C
Mix 1 hour, reaction solution is quenched with 250mL saturated aqueous ammonium chlorides, then extracted (100mL × 3) with methyl tertiary butyl ether(MTBE), merged
Organic phase, washed with 150mL saturated sodium-chloride water solutions, organic phase is concentrated under reduced pressure into dry, and residue column chromatography purifies to obtain formula
(1R, the 2R) shown in (1S, 2S) -2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl alcohol and Formula VII shown in VI -
2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl alcohol raceme 5.2g, yield 55%.High resolution mass spectrum (ESI+)：C12H27O2Si+ theoretical values 231.1775, measured value 231.1769.
(1R, 2R)-acetic acid 2- shown in (1S, 2S)-acetic acid 2- allyl basic ring propyl ester and Formula II shown in the Formulas I of embodiment 2
The preparation of allyl basic ring propyl ester raceme
Synthetic route is as follows：
(1) 2.0g 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl alcohol raceme is added into reaction bulb
(including shown in (1S, 2S) -2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl alcohol shown in Formula IV and Formula VII
(1R, 2R) -2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl alcohol), 30mL methyl tertiary butyl ether(MTBE)s and the second of 2.6g tri-
Amine (TEA), it is cooled to 0~10 DEG C and adds 1.4g chloroacetic chlorides (AcCl), be warming up to 20~30 DEG C and be stirred overnight, 20mL 1N are added dropwise
(mol/mL) aqueous hydrochloric acid solution, successively with 15mL saturated sodium bicarbonates and 15mL saturated common salt water washing organic phases, it is concentrated under reduced pressure
It is extremely dry, acquisition 2.2g acetic acid 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester raceme (including Formula VIII institute
(1R, the 2R) shown in (1S, 2S)-acetic acid 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester and Formula IX shown-
Acetic acid 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester), yield 93%.High resolution mass spectrum (ESI+)：
C14H29O3Si+ theoretical values 273.1880, measured value 273.1871.
(2) acetic acid 2- (3- ((t-Butyldimethylsilyl) epoxide) third prepared by 10g steps (1) are added into reaction bulb
Base) ring propyl ester raceme, it is dissolved in 80mL tetrahydrofurans, the tetrahydrofuran for adding 75mL tetra-n-butyls ammonium fluoride (TBAF) is molten
Liquid (1M tetrahydrofuran solutions), 20~30 DEG C of stirring 2h, adds the dilution of 300mL ethyl acetate, with 150mL 1N aqueous hydrochloric acid solutions
Washing, then 100mL saturated sodium bicarbonate aqueous solutions and 100mL saturated common salt water washings are used successively, it is concentrated under reduced pressure into dry, acquisition
5.3g acetic acid 2- (3- hydroxypropyls) ring propyl ester raceme (including (1S, 2S)-acetic acid 2- (3- hydroxypropyls) ring propyl ester shown in Formula X
With (1R, 2R)-acetic acid 2- (3- hydroxypropyls) ring propyl ester shown in Formula X I), yield 91%.High resolution mass spectrum (ESI+)：
C8H15O3+ theoretical values 159.1016, measured value 159.1010.
(3) acetic acid 2- (3- hydroxypropyls) ring propyl ester raceme prepared by 10g steps (2) is added into reaction bulb, is dissolved in
In 200mL glycol dimethyl ethers, 18g burgess reagent (Burgess reagents, N- (triethyl ammonium sulphonyl) carbamic acid are added
Methyl esters), 50 DEG C of reaction 1h are heated under nitrogen protection, are cooled to 20~30 DEG C, are added 300mL methyl tertiary butyl ether(MTBE)s, use
200mL saturated common salt water washings, with anhydrous sodium sulfate drying, it is concentrated under reduced pressure into dry, acquisition acetic acid 2- allyl basic ring propyl ester racemizations
Body (including (1S, 2S)-acetic acid 2- allyl basic ring propyl ester shown in Formulas I and (1R, 2R)-acetic acid 2- allyl basic rings shown in Formula II
Propyl ester) 7.7g, yield 87%.It is as shown in Figure 1 with magnetic resonance detection product, its hydrogen nuclear magnetic resonance spectrogram.
(1R, 2R)-acetic acid 2- shown in (1S, 2S)-acetic acid 2- allyl basic ring propyl ester and Formula II shown in the Formulas I of embodiment 3
The preparation of allyl basic ring propyl ester raceme
(1) 2.0g 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl alcohol raceme is added into reaction bulb
(including shown in (1S, 2S) -2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl alcohol shown in Formula IV and Formula VII
(1R, 2R) -2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl alcohol), 30mL methyl tertiary butyl ether(MTBE)s and the second of 2.0g tri-
Amine (TEA), it is cooled to 0~10 DEG C and adds 2.0g chloroacetic chlorides (AcCl), be warming up to 20~30 DEG C and be stirred overnight, 20mL 1N are added dropwise
(mol/mL) aqueous hydrochloric acid solution, successively with 15mL saturated sodium bicarbonates and 15mL saturated common salt water washing organic phases, it is concentrated under reduced pressure
It is extremely dry, acquisition 2.0g acetic acid 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester raceme (including Formula VIII institute
(1R, the 2R) shown in (1S, 2S)-acetic acid 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester and Formula IX shown-
Acetic acid 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester), yield 85%.High resolution mass spectrum (ESI+)：
C14H29O3Si+ theoretical values 273.1880, measured value 273.1871.
(2) acetic acid 2- (3- ((t-Butyldimethylsilyl) epoxide) third prepared by 10g steps (1) are added into reaction bulb
Base) ring propyl ester raceme, it is dissolved in 80mL tetrahydrofurans, the tetrahydrofuran for adding 60mL tetra-n-butyls ammonium fluoride (TBAF) is molten
Liquid (1M tetrahydrofuran solutions), 20~30 DEG C of stirring 2h, adds the dilution of 300mL ethyl acetate, with 150mL 1N aqueous hydrochloric acid solutions
Washing, then 100mL saturated sodium bicarbonate aqueous solutions and 100mL saturated common salt water washings are used successively, it is concentrated under reduced pressure into dry, acquisition
4.5g acetic acid 2- (3- hydroxypropyls) ring propyl ester raceme (including (1S, 2S)-acetic acid 2- (3- hydroxypropyls) ring propyl ester shown in Formula X
With (1R, 2R)-acetic acid 2- (3- hydroxypropyls) ring propyl ester shown in Formula X I), yield 85%.High resolution mass spectrum (ESI+)：
C8H15O3+ theoretical values 159.1016, measured value 159.1010.
(3) acetic acid 2- (3- hydroxypropyls) ring propyl ester raceme prepared by 10g steps (2) is added into reaction bulb, is dissolved in
In 200mL glycol dimethyl ethers, 10g burgess reagent (Burgess reagents, N- (triethyl ammonium sulphonyl) carbamic acid are added
Methyl esters), 50 DEG C of reaction 1h are heated under nitrogen protection, are cooled to 20~30 DEG C, are added 300mL methyl tertiary butyl ether(MTBE)s, use
200mL saturated common salt water washings, with anhydrous sodium sulfate drying, it is concentrated under reduced pressure into dry, acquisition acetic acid 2- allyl basic ring propyl ester racemizations
Body (including (1S, 2S)-acetic acid 2- allyl basic ring propyl ester shown in Formulas I and (1R, 2R)-acetic acid 2- allyl basic rings shown in Formula II
Propyl ester) 5.6g, yield 80%.
(1R, 2R)-acetic acid 2- shown in (1S, 2S)-acetic acid 2- allyl basic ring propyl ester and Formula II shown in the Formulas I of embodiment 4
The preparation of allyl basic ring propyl ester raceme
(1) 2.0g 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl alcohol raceme is added into reaction bulb
(including shown in (1S, 2S) -2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl alcohol shown in Formula IV and Formula VII
(1R, 2R) -2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl alcohol), 30mL methyl tertiary butyl ether(MTBE)s and 3g triethylamines
(TEA), it is cooled to 0~10 DEG C and adds 1g chloroacetic chlorides (AcCl), be warming up to 20~30 DEG C and be stirred overnight, 20mL 1N (mol/ is added dropwise
ML) aqueous hydrochloric acid solution, successively with 15mL saturated sodium bicarbonates and 15mL saturated common salt water washing organic phases, be concentrated under reduced pressure into it is dry,
Acquisition 1.5g acetic acid 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester raceme (including shown in Formula VIII
(1R, 2R)-acetic acid shown in (1S, 2S)-acetic acid 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester and Formula IX
2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester), yield 80%.High resolution mass spectrum (ESI+)：
C14H29O3Si+ theoretical values 273.1880, measured value 273.1871.
(2) acetic acid 2- (3- ((t-Butyldimethylsilyl) epoxide) third prepared by 10g steps (1) are added into reaction bulb
Base) ring propyl ester raceme, it is dissolved in 80mL tetrahydrofurans, the tetrahydrofuran for adding 90mL tetra-n-butyls ammonium fluoride (TBAF) is molten
Liquid (1M tetrahydrofuran solutions), 20~30 DEG C of stirring 2h, adds the dilution of 300mL ethyl acetate, with 150mL 1N aqueous hydrochloric acid solutions
Washing, then 100mL saturated sodium bicarbonate aqueous solutions and 100mL saturated common salt water washings are used successively, it is concentrated under reduced pressure into dry, acquisition
4.9g acetic acid 2- (3- hydroxypropyls) ring propyl ester raceme (including (1S, 2S)-acetic acid 2- (3- hydroxypropyls) ring propyl ester shown in Formula X
With (1R, 2R)-acetic acid 2- (3- hydroxypropyls) ring propyl ester shown in Formula X I), yield 87%.High resolution mass spectrum (ESI+)：
C8H15O3+ theoretical values 159.1016, measured value 159.1010.
(3) acetic acid 2- (3- hydroxypropyls) ring propyl ester raceme prepared by 10g steps (2) is added into reaction bulb, is dissolved in
In 200mL glycol dimethyl ethers, 30g burgess reagent (Burgess reagents, N- (triethyl ammonium sulphonyl) carbamic acid are added
Methyl esters), 50 DEG C of reaction 1h are heated under nitrogen protection, are cooled to 20~30 DEG C, are added 300mL methyl tertiary butyl ether(MTBE)s, use
200mL saturated common salt water washings, with anhydrous sodium sulfate drying, it is concentrated under reduced pressure into dry, acquisition acetic acid 2- allyl basic ring propyl ester racemizations
Body (including (1S, 2S)-acetic acid 2- allyl basic ring propyl ester shown in Formulas I and (1R, 2R)-acetic acid 2- allyl basic rings shown in Formula II
Propyl ester) 7.5g, yield 69%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (9)
1. a kind of synthetic method of acetic acid 2- allyls basic ring propyl ester raceme, it is characterised in that comprise the following steps：
(1) (1S, 2S) -2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl alcohol and (1R, 2R) -2- (3- ((tertiary fourths
Base dimethyl silicon substrate) epoxide) propyl group) ring propyl alcohol raceme through acetylation, obtains (1S, 2S)-acetic acid 2- (3- ((tert-butyl group diformazans
Base silicon substrate) epoxide) propyl group) ring propyl ester and (1R, 2R)-acetic acid 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester
Raceme；
(2) (1S, 2S)-acetic acid 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester and (1R, 2R)-acetic acid 2-
(3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester raceme obtains (1S, 2S)-acetic acid 2- through de- protected silane
(3- hydroxypropyls) ring propyl ester and (1R, 2R)-acetic acid 2- (3- hydroxypropyls) ring propyl ester raceme；
(3) (1S, 2S)-acetic acid 2- (3- hydroxypropyls) ring propyl ester and (1R, 2R)-acetic acid 2- (3- hydroxypropyls) ring propyl ester raceme pass through
Elimination reaction, obtain (1S, 2S)-acetic acid 2- allyl basic ring propyl ester and (1R, 2R)-acetic acid 2- allyl basic ring propyl ester racemies.
2. the synthetic method of acetic acid 2- allyls basic ring propyl ester raceme according to claim 1, it is characterised in that including with
Lower step：
(1) by (1S, 2S) -2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl alcohol and (1R, 2R) -2- (3- ((uncles
Butyldimethyl silicon substrate) epoxide) propyl group) and ring propyl alcohol raceme, methyl tertiary butyl ether(MTBE) and triethylamine be cooled to 0~10 DEG C addition second
Acyl chlorides, be stirred overnight after being warming up to 20~30 DEG C, be added dropwise aqueous hydrochloric acid solution, washing organic phase, be concentrated under reduced pressure into it is dry, obtain (1S,
2S)-acetic acid 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester and (1R, 2R)-acetic acid 2- (3- ((tert-butyl groups two
Methylsilyl) epoxide) propyl group) ring propyl ester raceme；
(2) by (1S, 2S)-acetic acid 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester and (1R, 2R)-acetic acid 2-
(3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester raceme is dissolved in tetrahydrofuran, adds tetra-n-butyl fluorination
The tetrahydrofuran solution of ammonium, 20~30 DEG C stirring 1~3h, through dilute, wash, be concentrated under reduced pressure into it is dry, obtain (1S, 2S)-acetic acid
2- (3- hydroxypropyls) ring propyl ester and (1R, 2R)-acetic acid 2- (3- hydroxypropyls) ring propyl ester raceme；
(3) by (1S, 2S)-acetic acid 2- (3- hydroxypropyls) ring propyl ester and (1R, 2R)-acetic acid 2- (3- hydroxypropyls) ring propyl ester raceme
It is dissolved in glycol dimethyl ether, adds burgess reagent, is heated to 40~60 DEG C of reaction 0.5-2h under nitrogen protection, is cooled to
20~30 DEG C, add methyl tertiary butyl ether(MTBE), it is scrubbed, drys, be concentrated under reduced pressure into it is dry, acquisition (1S, 2S)-acetic acid 2- allyl basic rings
Propyl ester and (1R, 2R)-acetic acid 2- allyl basic ring propyl ester racemies.
3. the synthetic method of acetic acid 2- allyls basic ring propyl ester raceme according to claim 2, it is characterised in that in step
(1) in, (1S, 2S) -2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl alcohol and (1R, 2R) -2- (3- ((tert-butyl groups
Dimethyl silicon substrate) epoxide) propyl group) ring propyl alcohol raceme：Triethylamine：The mass ratio of chloroacetic chloride is 1~2:1~3:1.
4. the synthetic method of acetic acid 2- allyls basic ring propyl ester raceme according to claim 2, it is characterised in that in step
(1) in, the process of the washing is to use saturated sodium bicarbonate and saturated common salt water washing successively.
5. the synthetic method of acetic acid 2- allyls basic ring propyl ester raceme according to claim 2, it is characterised in that in step
(2) in, every 1g (1S, 2S)-acetic acid 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester and (1R, 2R)-acetic acid
The four of 6~9mL tetra-n-butyl ammonium fluorides is added in 2- (3- ((t-Butyldimethylsilyl) epoxide) propyl group) ring propyl ester raceme
Hydrogen tetrahydrofuran solution.
6. the synthetic method of acetic acid 2- allyls basic ring propyl ester raceme according to claim 2, it is characterised in that in step
(2) in, the reagent of the dilution is ethyl acetate；And/or
The process of the washing is first to be washed with aqueous hydrochloric acid solution, then uses saturated sodium bicarbonate aqueous solution and saturated aqueous common salt successively
Washing.
7. the synthetic method of acetic acid 2- allyls basic ring propyl ester raceme according to claim 2, it is characterised in that in step
(3) in, (1S, 2S)-acetic acid 2- (3- hydroxypropyls) ring propyl ester and (1R, 2R)-acetic acid 2- (3- hydroxypropyls) ring propyl ester raceme：Primary
The mass ratio of this lucky reagent is 1:1~3.
8. the synthetic method of acetic acid 2- allyls basic ring propyl ester raceme according to claim 2, it is characterised in that in step
(3) in, the reagent of the washing is saturated aqueous common salt；And/or
It is described dry that reagent is anhydrous sodium sulfate.
9. prepared by the acetic acid 2- allyl basic ring propyl ester racemies that the synthetic method any one of claim 1 to 8 obtains
Purposes in Fu Xiruiwei.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5929291A (en) * | 1996-04-09 | 1999-07-27 | Givaudan Roure (International) Sa | Odorants |
| CN103450313A (en) * | 2013-08-21 | 2013-12-18 | 苏州明锐医药科技有限公司 | Preparation method of abiraterone acetate |
| CN105849118A (en) * | 2013-12-23 | 2016-08-10 | 吉利德科学公司 | Synthesis of a macrocyclic HCV NS3 inhibiting tripeptide |
-
2017
- 2017-11-14 CN CN201711126406.4A patent/CN107827748A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5929291A (en) * | 1996-04-09 | 1999-07-27 | Givaudan Roure (International) Sa | Odorants |
| CN103450313A (en) * | 2013-08-21 | 2013-12-18 | 苏州明锐医药科技有限公司 | Preparation method of abiraterone acetate |
| CN105849118A (en) * | 2013-12-23 | 2016-08-10 | 吉利德科学公司 | Synthesis of a macrocyclic HCV NS3 inhibiting tripeptide |
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