JP4686701B2 - 金属−ジアミン錯体及びそれを用いた不斉カップリング方法 - Google Patents
金属−ジアミン錯体及びそれを用いた不斉カップリング方法 Download PDFInfo
- Publication number
- JP4686701B2 JP4686701B2 JP2004011110A JP2004011110A JP4686701B2 JP 4686701 B2 JP4686701 B2 JP 4686701B2 JP 2004011110 A JP2004011110 A JP 2004011110A JP 2004011110 A JP2004011110 A JP 2004011110A JP 4686701 B2 JP4686701 B2 JP 4686701B2
- Authority
- JP
- Japan
- Prior art keywords
- octahydrobisisoquinoline
- metal
- formula
- complex
- naphthol derivative
- 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.)
- Expired - Lifetime
Links
- 238000010168 coupling process Methods 0.000 title claims description 15
- 150000004786 2-naphthols Chemical class 0.000 claims description 18
- 238000005859 coupling reaction Methods 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 230000008878 coupling Effects 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 150000002736 metal compounds Chemical class 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 150000004780 naphthols Chemical class 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000002821 niobium Chemical class 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- IOEPOEDBBPRAEI-UHFFFAOYSA-N 1,2-dihydroisoquinoline Chemical compound C1=CC=C2CNC=CC2=C1 IOEPOEDBBPRAEI-UHFFFAOYSA-N 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 235000002597 Solanum melongena Nutrition 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 150000001879 copper Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UWYZHKAOTLEWKK-UHFFFAOYSA-N 1,2,3,4-tetrahydroisoquinoline Chemical compound C1=CC=C2CNCCC2=C1 UWYZHKAOTLEWKK-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- NKSZCPBUWGZONP-UHFFFAOYSA-N 3,4-dihydroisoquinoline Chemical compound C1=CC=C2C=NCCC2=C1 NKSZCPBUWGZONP-UHFFFAOYSA-N 0.000 description 2
- -1 Copper halide Chemical class 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- SEZHLKZEWYFCRB-UHFFFAOYSA-N 1,2-dimethoxyethane;oxolane Chemical compound C1CCOC1.COCCOC SEZHLKZEWYFCRB-UHFFFAOYSA-N 0.000 description 1
- 102100027324 2-hydroxyacyl-CoA lyase 1 Human genes 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 101001009252 Homo sapiens 2-hydroxyacyl-CoA lyase 1 Proteins 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 229960002510 mandelic acid Drugs 0.000 description 1
- YVVBECLPRBAATK-UHFFFAOYSA-N methyl 3-hydroxynaphthalene-2-carboxylate Chemical compound C1=CC=C2C=C(O)C(C(=O)OC)=CC2=C1 YVVBECLPRBAATK-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- DSYRJFDOOSKABR-UHFFFAOYSA-I niobium(v) bromide Chemical compound [Br-].[Br-].[Br-].[Br-].[Br-].[Nb+5] DSYRJFDOOSKABR-UHFFFAOYSA-I 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- FWIYBTVHGYLSAZ-UHFFFAOYSA-I pentaiodoniobium Chemical compound I[Nb](I)(I)(I)I FWIYBTVHGYLSAZ-UHFFFAOYSA-I 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- XOJVVFBFDXDTEG-UHFFFAOYSA-N pristane Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Other In-Based Heterocyclic Compounds (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
1H-NMR(CDCl3,400MHz)δ:2.60(2H,d,J=15.2Hz),2.80(2H,dt,J=3.2,11.5Hz),2.88-2.96(2H,m),3.18(2H,ddd,J=2.4,5.2,11.5Hz),4.68(2H,s),7.10(2H,d,J=7.2Hz,),7.15(2H,t,J=7.2Hz),7.21(2H,t,J=7.6Hz),7.36(2H,d,J=7.6Hz)
13C-NMR(CDCl3,100MHz)δ:30.4,42.8,60.1,125.1,126.0,126.2,129.3,136.6,137.3
mp113-114℃
(1S,1'S)[α]D 22,+254.8(c1.07,CHCl3)>99%ee
(1R,1'R)[α]D 22,-251.0(c1.02,CHCl3)>99%ee
*HPCL condition; カラム:DAICEL CHIRALCEL OD(ダイセル化学工業製), 移動相:Hexane/iPrOH=9/1, 流速:0.5mL/min, R.t.:17.7min(1S,1'S),27.5min(1R,1'R)
1H-NMR(CDCl3,400MHz,)d:4.05(6H,s),7.14-7.16(2H,m)7.32-7.35(4H,m)7.90-7.93(2H,m)8.68(2H,s),10.7(2H,s)
*HPLC conditions; カラム:DAICEL CHIRALPAC AD(ダイセル化学工業製), 移動相:Hexane/iPrOH=9/1, 流速: 1.0ml/min, R.t.:9.4min(S),15.5min(R)
Claims (5)
- (+)−オクタヒドロ−1,1’−ビスイソキノリンに塩化銅を添加して形成される銅−オクタヒドロ−1,1’−ビスイソキノリン錯体。
- (−)−オクタヒドロ−1,1’−ビスイソキノリンに塩化銅を添加して形成される銅−オクタヒドロ−1,1’−ビスイソキノリン錯体。
- 請求項1又は2に記載の錯体を触媒とし、2−ナフトール誘導体を酸化的に不斉カップリングすることを特徴とする不斉カップリング方法。
- 請求項2に記載の錯体を形成する工程と、前記錯体に下記式で示される2−ナフトール誘導体を添加することにより前記2−ナフトール誘導体をカップリング反応させて選択的に下記式で表される(R)−isomerを得る工程を具備することを特徴とする2−ナフトール誘導体の不斉カップリング方法。
- 請求項1に記載の錯体を形成する工程と、前記錯体に下記式で示される2−ナフトール誘導体を添加することにより前記2−ナフトール誘導体をカップリング反応させて選択的に下記式で表される(S)−isomerを得る工程を具備することを特徴とする2−ナフトール誘導体の不斉カップリング方法。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004011110A JP4686701B2 (ja) | 2004-01-19 | 2004-01-19 | 金属−ジアミン錯体及びそれを用いた不斉カップリング方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004011110A JP4686701B2 (ja) | 2004-01-19 | 2004-01-19 | 金属−ジアミン錯体及びそれを用いた不斉カップリング方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2005200388A JP2005200388A (ja) | 2005-07-28 |
JP4686701B2 true JP4686701B2 (ja) | 2011-05-25 |
Family
ID=34823633
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2004011110A Expired - Lifetime JP4686701B2 (ja) | 2004-01-19 | 2004-01-19 | 金属−ジアミン錯体及びそれを用いた不斉カップリング方法 |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4686701B2 (ja) |
-
2004
- 2004-01-19 JP JP2004011110A patent/JP4686701B2/ja not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JP2005200388A (ja) | 2005-07-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103087105B (zh) | 手性膦配体以及包含该配体的金属催化剂和它们的应用 | |
CN101993406B (zh) | 光学活性的吲哚啉化合物及其制备方法 | |
CN110041174B (zh) | 一种ebinol轴手性化合物及其合成方法和应用 | |
JP4718452B2 (ja) | 光学活性遷移金属−ジアミン錯体及びこれを用いた光学活性アルコール類の製造方法 | |
TWI582098B (zh) | 有機硼化合物及製造彼之方法 | |
JP4194865B2 (ja) | エナンチオマーが富化されたアリールアミノプロパノールの製造方法 | |
CN104447234A (zh) | (3r,4r)-4-(3,4-二甲氧基苄基)-3-(4-羟基-3-甲氧基苄基)-二氢呋喃的制备方法 | |
AU2011301115B2 (en) | Biaryl diphosphine ligands, intermediates of the same and their use in asymmetric catalysis | |
WO2005007662A2 (en) | Biphosphine ruthenium complexes with chiral diamine ligande as catalysts | |
JP5271503B2 (ja) | 有機ホウ素化合物の製造方法 | |
CN105026370B (zh) | 取代的吡咯烷‑2‑甲酰胺的不对称合成 | |
JP2008526940A (ja) | 置換されたプロピオン酸類を製造するための方法 | |
JP4686701B2 (ja) | 金属−ジアミン錯体及びそれを用いた不斉カップリング方法 | |
JP4617457B2 (ja) | ラセミ体オクタヒドロビスイソキノリンの製造方法及び光学活性オクタヒドロビスイソキノリンの製造方法並びに光学活性オクタヒドロビスイソキノリン | |
Taniguchi et al. | Solvent control of optical resolution of 2-amino-1-phenylethanol using dehydroabietic acid | |
WO2008135386A1 (fr) | Ligands chiraux de type carbenes n-heterocycliques pour la catalyse asymetrique | |
JP5335997B2 (ja) | 2−ブロモ−6−フルオロナフタレンの調製方法 | |
JP2012056876A (ja) | ジカルボニル化合物、その中間体及びその製造方法 | |
JP4425654B2 (ja) | 水溶性遷移金属−ジアミン錯体、及びその製造方法、並びにその用途 | |
CN109553595A (zh) | 一种手性γ-丁内酯的制备方法及其中间体 | |
JP3912818B2 (ja) | キラルα−ハロゲンカルボン酸の製造方法 | |
JP7431155B2 (ja) | テトラヒドロナフチルウレア誘導体の製造方法 | |
CA2835459C (fr) | Nouveau procede de synthese du 3-(2-bromo-4,5-dimethoxyphenyl)propanenitrile, et application a la synthese de l'ivabradine et de ses sels d'addition a un acide pharmaceutiquement acceptable | |
CN109020895B (zh) | 一种金属催化的1-苄胺基取代苯并咪唑的合成方法 | |
WO2002040492A1 (fr) | Diphosphines chirales et leurs complexes metalliques |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070119 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100421 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100518 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100720 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20101005 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101118 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110118 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 4686701 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
EXPY | Cancellation because of completion of term |