CN103641808B - 色烯的对映选择性氢化方法 - Google Patents
色烯的对映选择性氢化方法 Download PDFInfo
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- CN103641808B CN103641808B CN201310533995.3A CN201310533995A CN103641808B CN 103641808 B CN103641808 B CN 103641808B CN 201310533995 A CN201310533995 A CN 201310533995A CN 103641808 B CN103641808 B CN 103641808B
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- Prior art keywords
- phenyl
- equol
- chroman
- chromene
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- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 26
- QZHPTGXQGDFGEN-UHFFFAOYSA-N chromene Chemical compound C1=CC=C2C=C[CH]OC2=C1 QZHPTGXQGDFGEN-UHFFFAOYSA-N 0.000 title claims description 15
- ADFCQWZHKCXPAJ-GFCCVEGCSA-N equol Chemical compound C1=CC(O)=CC=C1[C@@H]1CC2=CC=C(O)C=C2OC1 ADFCQWZHKCXPAJ-GFCCVEGCSA-N 0.000 claims abstract description 71
- ADFCQWZHKCXPAJ-UHFFFAOYSA-N indofine Natural products C1=CC(O)=CC=C1C1CC2=CC=C(O)C=C2OC1 ADFCQWZHKCXPAJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003446 ligand Substances 0.000 claims abstract description 34
- 235000019126 equol Nutrition 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims description 40
- ZQSIJRDFPHDXIC-UHFFFAOYSA-N daidzein Chemical group C1=CC(O)=CC=C1C1=COC2=CC(O)=CC=C2C1=O ZQSIJRDFPHDXIC-UHFFFAOYSA-N 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 30
- -1 chroman-ol compound Chemical class 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- 235000007240 daidzein Nutrition 0.000 claims description 16
- 229910052741 iridium Inorganic materials 0.000 claims description 15
- 230000002829 reductive effect Effects 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- CNNBJLXLTIKXGJ-UHFFFAOYSA-N 3-phenyl-2h-chromene Chemical compound C1OC2=CC=CC=C2C=C1C1=CC=CC=C1 CNNBJLXLTIKXGJ-UHFFFAOYSA-N 0.000 claims description 6
- MSTDXOZUKAQDRL-UHFFFAOYSA-N 4-Chromanone Chemical compound C1=CC=C2C(=O)CCOC2=C1 MSTDXOZUKAQDRL-UHFFFAOYSA-N 0.000 claims description 6
- FVOOPOSZDXPIMS-UHFFFAOYSA-N 3,4-dihydro-2h-chromen-2-ol Chemical compound C1=CC=C2OC(O)CCC2=C1 FVOOPOSZDXPIMS-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- HKQYGTCOTHHOMP-UHFFFAOYSA-N formononetin Chemical compound C1=CC(OC)=CC=C1C1=COC2=CC(O)=CC=C2C1=O HKQYGTCOTHHOMP-UHFFFAOYSA-N 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- KYNSBQPICQTCGU-UHFFFAOYSA-N Benzopyrane Chemical compound C1=CC=C2C=CCOC2=C1 KYNSBQPICQTCGU-UHFFFAOYSA-N 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 3
- RYIOLWQRQXDECZ-UHFFFAOYSA-N phosphinous acid Chemical compound PO RYIOLWQRQXDECZ-UHFFFAOYSA-N 0.000 claims 3
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- OTAFHZMPRISVEM-UHFFFAOYSA-N chromone Chemical compound C1=CC=C2C(=O)C=COC2=C1 OTAFHZMPRISVEM-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 23
- 150000008371 chromenes Chemical class 0.000 abstract description 8
- NHFAABIHBNXKDT-UHFFFAOYSA-N 4,5-dihydro-1,3-oxazole;phosphane Chemical compound P.C1CN=CO1 NHFAABIHBNXKDT-UHFFFAOYSA-N 0.000 abstract description 7
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 abstract description 7
- 150000001843 chromanes Chemical class 0.000 abstract description 7
- 230000000707 stereoselective effect Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 abstract description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 102
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 81
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 65
- 239000000047 product Substances 0.000 description 61
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 41
- 239000007787 solid Substances 0.000 description 38
- 238000001228 spectrum Methods 0.000 description 38
- 239000000243 solution Substances 0.000 description 35
- 235000019439 ethyl acetate Nutrition 0.000 description 31
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 26
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- ADFCQWZHKCXPAJ-LBPRGKRZSA-N (R)-Equol Chemical compound C1=CC(O)=CC=C1[C@H]1CC2=CC=C(O)C=C2OC1 ADFCQWZHKCXPAJ-LBPRGKRZSA-N 0.000 description 21
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 239000007858 starting material Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- ZZUBHVMHNVYXRR-UHFFFAOYSA-N Dehydroequol Natural products C1=CC(O)=CC=C1C1=CC2=CC=C(O)C=C2OC1 ZZUBHVMHNVYXRR-UHFFFAOYSA-N 0.000 description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 13
- 229910052938 sodium sulfate Inorganic materials 0.000 description 13
- 235000011152 sodium sulphate Nutrition 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 239000000741 silica gel Substances 0.000 description 12
- 229910002027 silica gel Inorganic materials 0.000 description 12
- 239000012044 organic layer Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- VZWXIQHBIQLMPN-UHFFFAOYSA-N chromane Chemical compound C1=CC=C2CCCOC2=C1 VZWXIQHBIQLMPN-UHFFFAOYSA-N 0.000 description 9
- 239000003480 eluent Substances 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 239000000543 intermediate Substances 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 125000006239 protecting group Chemical group 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000010511 deprotection reaction Methods 0.000 description 6
- 239000013067 intermediate product Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- AYFVYJQAPQTCCC-STHAYSLISA-N D-threonine Chemical compound C[C@H](O)[C@@H](N)C(O)=O AYFVYJQAPQTCCC-STHAYSLISA-N 0.000 description 5
- 229930182822 D-threonine Natural products 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 238000004949 mass spectrometry Methods 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- MGSHXMOLUWTMGP-UHFFFAOYSA-N 3'-carboxy-alpha-chromanol Chemical compound C1=CC=C2C(O)CCOC2=C1 MGSHXMOLUWTMGP-UHFFFAOYSA-N 0.000 description 3
- BKTYTXGJSMWNTG-UHFFFAOYSA-N 7-(methoxymethoxy)-3-[4-(methoxymethoxy)phenyl]-2h-chromene Chemical compound C1=CC(OCOC)=CC=C1C1=CC2=CC=C(OCOC)C=C2OC1 BKTYTXGJSMWNTG-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 description 3
- 235000010469 Glycine max Nutrition 0.000 description 3
- 244000068988 Glycine max Species 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
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- 230000001076 estrogenic effect Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
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- GOMNOOKGLZYEJT-UHFFFAOYSA-N isoflavone Chemical compound C=1OC2=CC=CC=C2C(=O)C=1C1=CC=CC=C1 GOMNOOKGLZYEJT-UHFFFAOYSA-N 0.000 description 3
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- 239000010410 layer Substances 0.000 description 3
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- TVHCXXXXQNWQLP-IUYQGCFVSA-N methyl (2r,3s)-2-amino-3-hydroxybutanoate Chemical compound COC(=O)[C@H](N)[C@H](C)O TVHCXXXXQNWQLP-IUYQGCFVSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 2
- VMUXSMXIQBNMGZ-UHFFFAOYSA-N 3,4-dihydrocoumarin Chemical class C1=CC=C2OC(=O)CCC2=C1 VMUXSMXIQBNMGZ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium on carbon Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
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- 238000001212 derivatisation Methods 0.000 description 2
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- 125000000623 heterocyclic group Chemical group 0.000 description 2
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- RTRZOHKLISMNRD-UHFFFAOYSA-N isoflavanone Chemical compound C1OC2=CC=CC=C2C(=O)C1C1=CC=CC=C1 RTRZOHKLISMNRD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- KHOWDUMYRBCHAC-WCBMZHEXSA-N methyl (2r,3s)-2-benzamido-3-hydroxybutanoate Chemical compound COC(=O)[C@@H]([C@H](C)O)NC(=O)C1=CC=CC=C1 KHOWDUMYRBCHAC-WCBMZHEXSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- UISYECGDYFSVFI-UHFFFAOYSA-N 7-(methoxymethoxy)-3-[4-(methoxymethoxy)phenyl]-2,3-dihydrochromen-4-one Chemical class C1=CC(OCOC)=CC=C1C1C(=O)C2=CC=C(OCOC)C=C2OC1 UISYECGDYFSVFI-UHFFFAOYSA-N 0.000 description 1
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- 0 C*1=CC(*)=CC(*)C1 Chemical compound C*1=CC(*)=CC(*)C1 0.000 description 1
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- QRKUHYFDBWGLHJ-UHFFFAOYSA-N N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide Chemical compound FC(F)(F)C(=O)N(C)[Si](C)(C)C(C)(C)C QRKUHYFDBWGLHJ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- NAKBTSWRNHJUPM-UHFFFAOYSA-N O=Nc1ccc(C(C2)COc3c2ccc(N=O)c3)cc1 Chemical compound O=Nc1ccc(C(C2)COc3c2ccc(N=O)c3)cc1 NAKBTSWRNHJUPM-UHFFFAOYSA-N 0.000 description 1
- 206010067572 Oestrogenic effect Diseases 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- 235000015724 Trifolium pratense Nutrition 0.000 description 1
- 241000212749 Zesius chrysomallus Species 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 238000004296 chiral HPLC Methods 0.000 description 1
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 1
- 229940061627 chloromethyl methyl ether Drugs 0.000 description 1
- 150000004777 chromones Chemical class 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000013058 crude material Substances 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000000378 dietary effect Effects 0.000 description 1
- 230000006806 disease prevention Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003821 enantio-separation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000006539 genistein Nutrition 0.000 description 1
- TZBJGXHYKVUXJN-UHFFFAOYSA-N genistein Natural products C1=CC(O)=CC=C1C1=COC2=CC(O)=CC(O)=C2C1=O TZBJGXHYKVUXJN-UHFFFAOYSA-N 0.000 description 1
- 229940045109 genistein Drugs 0.000 description 1
- ZCOLJUOHXJRHDI-CMWLGVBASA-N genistein 7-O-beta-D-glucoside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=C2C(=O)C(C=3C=CC(O)=CC=3)=COC2=C1 ZCOLJUOHXJRHDI-CMWLGVBASA-N 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 150000008131 glucosides Chemical class 0.000 description 1
- 229930182480 glucuronide Natural products 0.000 description 1
- 150000008134 glucuronides Chemical class 0.000 description 1
- 244000005709 gut microbiome Species 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- GGQOPZKTDHXXON-UHFFFAOYSA-N hexane;methanol Chemical compound OC.CCCCCC GGQOPZKTDHXXON-UHFFFAOYSA-N 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical class [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- SCEZYJKGDJPHQO-UHFFFAOYSA-M magnesium;methanidylbenzene;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C1=CC=CC=C1 SCEZYJKGDJPHQO-UHFFFAOYSA-M 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- IZDROVVXIHRYMH-UHFFFAOYSA-N methanesulfonic anhydride Chemical compound CS(=O)(=O)OS(C)(=O)=O IZDROVVXIHRYMH-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 125000004092 methylthiomethyl group Chemical group [H]C([H])([H])SC([H])([H])* 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- KAVKNHPXAMTURG-UHFFFAOYSA-N n-(4-bromonaphthalen-1-yl)acetamide Chemical compound C1=CC=C2C(NC(=O)C)=CC=C(Br)C2=C1 KAVKNHPXAMTURG-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000000820 nonprescription drug Substances 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 125000005538 phosphinite group Chemical group 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000013526 red clover Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004007 reversed phase HPLC Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012056 semi-solid material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 235000003687 soy isoflavones Nutrition 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 150000003555 thioacetals Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000009901 transfer hydrogenation reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/34—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 3 only
- C07D311/38—2,3-Dihydro derivatives, e.g. isoflavanones
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyrane Compounds (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/194,280 US7528267B2 (en) | 2005-08-01 | 2005-08-01 | Method for enantioselective hydrogenation of chromenes |
| US11/194,280 | 2005-08-01 | ||
| CN200680036577.1A CN101535286B (zh) | 2005-08-01 | 2006-08-01 | 色烯的对映选择性氢化方法 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200680036577.1A Division CN101535286B (zh) | 2005-08-01 | 2006-08-01 | 色烯的对映选择性氢化方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103641808A CN103641808A (zh) | 2014-03-19 |
| CN103641808B true CN103641808B (zh) | 2016-04-20 |
Family
ID=37695254
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310533995.3A Expired - Fee Related CN103641808B (zh) | 2005-08-01 | 2006-08-01 | 色烯的对映选择性氢化方法 |
| CN201310655782.8A Expired - Fee Related CN103755675B (zh) | 2005-08-01 | 2006-08-01 | 色烯的对映选择性氢化方法 |
| CN200680036577.1A Expired - Fee Related CN101535286B (zh) | 2005-08-01 | 2006-08-01 | 色烯的对映选择性氢化方法 |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310655782.8A Expired - Fee Related CN103755675B (zh) | 2005-08-01 | 2006-08-01 | 色烯的对映选择性氢化方法 |
| CN200680036577.1A Expired - Fee Related CN101535286B (zh) | 2005-08-01 | 2006-08-01 | 色烯的对映选择性氢化方法 |
Country Status (8)
| Country | Link |
|---|---|
| US (4) | US7528267B2 (enExample) |
| EP (1) | EP1919887B1 (enExample) |
| JP (1) | JP5507081B2 (enExample) |
| CN (3) | CN103641808B (enExample) |
| AU (1) | AU2006275587B2 (enExample) |
| CA (1) | CA2617665C (enExample) |
| DK (1) | DK1919887T3 (enExample) |
| WO (1) | WO2007016423A2 (enExample) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2504682A1 (en) | 2002-10-29 | 2004-05-13 | Colorado State University Research Foundation | Use of equol for treating androgen mediated diseases |
| GB0610804D0 (en) * | 2006-05-31 | 2006-07-12 | Portela & Ca Sa | New crystal forms |
| US7714348B2 (en) * | 2006-10-06 | 2010-05-11 | Ac-Led Lighting, L.L.C. | AC/DC light emitting diodes with integrated protection mechanism |
| WO2008153158A1 (ja) * | 2007-06-13 | 2008-12-18 | Otsuka Pharmaceutical Co., Ltd. | エクオール含有抽出物及びその製造方法、エクオール抽出方法、並びにエクオールを含む食品 |
| EP2231648A1 (en) * | 2007-12-05 | 2010-09-29 | BIAL - Portela & Ca., S.A. | New salts and crystal forms |
| EP2133080A1 (de) | 2008-06-13 | 2009-12-16 | Haelan Schweiz GmbH | Zusammensetzungen enthaltend Equol |
| RU2364442C1 (ru) * | 2008-06-30 | 2009-08-20 | Государственное образовательное учреждение высшего профессионального образования "Тверской государственный технический университет" | Способ приготовления модифицированного платинового катализатора для энантиоселективного гидрирования сложных эфиров альфа-кетокарбоновых кислот |
| EP2154133A1 (de) | 2008-08-14 | 2010-02-17 | System Biologie AG | Synthese von Equol |
| US20110091435A1 (en) * | 2008-10-24 | 2011-04-21 | University Of Southern California | Phytoestrogenic formulations for alleviation or prevention of hair loss |
| US7875736B2 (en) * | 2009-05-19 | 2011-01-25 | Kaohsiung Medical University | Intermediate compounds and processes for the preparation of 7-benzyloxy-3-(4-methoxyphenyl)-2H-1-benzopyran |
| US7875735B2 (en) * | 2009-05-19 | 2011-01-25 | Kaohsiung Medical University | Processes for preparing isoflavonoids using 7-benzyloxy-3-(4-methoxyphenyl)-2H-1-benzopyran as a starting material |
| WO2011034126A1 (ja) * | 2009-09-18 | 2011-03-24 | 不二製油株式会社 | エクオールの不斉合成法 |
| CN102633763B (zh) * | 2012-04-11 | 2014-02-26 | 黑龙江大学 | 一种(s)-雌马酚的制备方法 |
| PL2953938T3 (pl) | 2014-02-07 | 2017-12-29 | Novogen Ltd. | Funkcjonalizowane związki benzopiranowe i ich zastosowanie |
| US10030003B2 (en) | 2014-09-10 | 2018-07-24 | System Biologie Ag | Synthesis of isoflavanes and intermediates thereof |
| US9914718B2 (en) * | 2014-10-14 | 2018-03-13 | Ausio Pharmaceuticals, Llc | Anhydrous crystalline form of S-equol |
| US10391079B2 (en) | 2016-07-26 | 2019-08-27 | Ausio Pharmaceuticals, Llc | Methods of diagnosing and treating Alzheimer's disease with S-equol |
| AU2019285640A1 (en) | 2018-06-15 | 2021-01-21 | Board Of Regents Of The University Of Texas System | Methods of treating and preventing breast cancer with S-equol |
| AU2019285641A1 (en) | 2018-06-15 | 2021-04-08 | The Board Of Regents Of The University Of Texas System | Methods of treating and preventing melanoma with s-equol |
| KR102819124B1 (ko) * | 2018-10-02 | 2025-06-12 | 주식회사 글라세움 | 탄소 이중결합 함유 화합물의 비대칭 수소첨가 반응용 촉매 |
| WO2020071818A1 (ko) * | 2018-10-02 | 2020-04-09 | 주식회사 글라세움 | 탄소 이중결합 함유 화합물의 비대칭 수소첨가 반응용 촉매 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1340048A (zh) * | 1999-02-15 | 2002-03-13 | 诺沃根研究有限公司 | 异黄酮衍生物的制备 |
| WO2004056349A2 (en) * | 2002-12-19 | 2004-07-08 | Pharmacia Corporation | Methods and compositions for the treatment of herpes virus infections using cyclooxygenase-2 selective inhibitors or cyclooxygenase-2 inhibitors in combination with antiviral agents |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4264509A (en) * | 1977-06-08 | 1981-04-28 | Z-L Limited Partnership | Isoflavones and related compounds, methods of preparing and using and antioxidant compositions containing same |
| GB8626344D0 (en) | 1986-11-04 | 1986-12-03 | Zyma Sa | Bicyclic compounds |
| AUPO203996A0 (en) * | 1996-08-30 | 1996-09-26 | Novogen Research Pty Ltd | Therapeutic uses |
| KR20000057548A (ko) * | 1996-12-13 | 2000-09-25 | 알프레드 엘. 미첼슨 | 광학적 전송물질 및 결합재 |
| JP4004547B2 (ja) * | 1997-03-06 | 2007-11-07 | 三井化学株式会社 | 光学活性アミンの製造方法 |
| US6576772B1 (en) * | 1999-11-10 | 2003-06-10 | The Penn State Research Foundation | Chiral phosphines, transition metal complexes thereof and uses thereof in asymmetric reactions |
| SE9904850D0 (sv) * | 1999-12-30 | 1999-12-30 | Pharmacia & Upjohn Ab | Novel process and intermediates |
| DE10044091A1 (de) * | 2000-09-07 | 2002-04-04 | Merck Patent Gmbh | Chromanonderivate |
| ATE294806T1 (de) * | 2000-09-21 | 2005-05-15 | Solvias Ag | Phosphinite-oxazoline und metallkomplexe |
| EP1427858A2 (en) | 2001-09-12 | 2004-06-16 | F. Hoffmann-La Roche Ag | Specific markers for multiple sclerosis |
| CA2492754C (en) * | 2002-07-24 | 2018-05-22 | Children's Hospital Medical Center | Compositions and products containing enantiomeric equol, and methods for their making |
| DE10237648A1 (de) | 2002-08-13 | 2004-02-26 | Behr Gmbh & Co. | Wärmeübertrager |
| CA2504682A1 (en) | 2002-10-29 | 2004-05-13 | Colorado State University Research Foundation | Use of equol for treating androgen mediated diseases |
| AU2002952453A0 (en) | 2002-11-01 | 2002-11-21 | Novogen Research Pty Ltd | Aminated isoflavonoid derivatives and uses thereof |
| ITMI20031354A1 (it) | 2003-07-02 | 2005-01-03 | Istituto Di Chimica Biomolecolare D El Cnr Sezione | Sintesis enantioselettiva di composti enantiomericamente arricchiti. |
-
2005
- 2005-08-01 US US11/194,280 patent/US7528267B2/en active Active
-
2006
- 2006-08-01 EP EP06788891.7A patent/EP1919887B1/en not_active Not-in-force
- 2006-08-01 DK DK06788891.7T patent/DK1919887T3/en active
- 2006-08-01 AU AU2006275587A patent/AU2006275587B2/en not_active Ceased
- 2006-08-01 CN CN201310533995.3A patent/CN103641808B/zh not_active Expired - Fee Related
- 2006-08-01 JP JP2008525065A patent/JP5507081B2/ja not_active Expired - Fee Related
- 2006-08-01 CN CN201310655782.8A patent/CN103755675B/zh not_active Expired - Fee Related
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- 2006-08-01 WO PCT/US2006/029589 patent/WO2007016423A2/en not_active Ceased
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2009
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2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1340048A (zh) * | 1999-02-15 | 2002-03-13 | 诺沃根研究有限公司 | 异黄酮衍生物的制备 |
| WO2004056349A2 (en) * | 2002-12-19 | 2004-07-08 | Pharmacia Corporation | Methods and compositions for the treatment of herpes virus infections using cyclooxygenase-2 selective inhibitors or cyclooxygenase-2 inhibitors in combination with antiviral agents |
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| Iridium-Catalyzed Enantioselective Hydrogenation of Olefins;Andreas Pfaltz，等;《Adv.Synth.Catal.》;20030121;第345卷(第1-2期);第41页图12 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5507081B2 (ja) | 2014-05-28 |
| CN101535286A (zh) | 2009-09-16 |
| CN103755675B (zh) | 2015-11-18 |
| WO2007016423A3 (en) | 2009-04-30 |
| EP1919887B1 (en) | 2015-02-18 |
| CA2617665A1 (en) | 2007-02-08 |
| US8716497B2 (en) | 2014-05-06 |
| US20120004427A1 (en) | 2012-01-05 |
| CN103755675A (zh) | 2014-04-30 |
| DK1919887T3 (en) | 2015-05-26 |
| US8263790B2 (en) | 2012-09-11 |
| CN101535286B (zh) | 2014-05-07 |
| US7528267B2 (en) | 2009-05-05 |
| AU2006275587B2 (en) | 2012-09-13 |
| EP1919887A4 (en) | 2011-01-19 |
| US20070027329A1 (en) | 2007-02-01 |
| CA2617665C (en) | 2014-12-02 |
| US20100069653A1 (en) | 2010-03-18 |
| CN103641808A (zh) | 2014-03-19 |
| WO2007016423A2 (en) | 2007-02-08 |
| AU2006275587A1 (en) | 2007-02-08 |
| JP2009503079A (ja) | 2009-01-29 |
| EP1919887A2 (en) | 2008-05-14 |
| US20130116450A1 (en) | 2013-05-09 |
| US7960573B2 (en) | 2011-06-14 |
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