JP6065259B2 - 光学活性アミン類の製造方法 - Google Patents
光学活性アミン類の製造方法 Download PDFInfo
- Publication number
- JP6065259B2 JP6065259B2 JP2012197246A JP2012197246A JP6065259B2 JP 6065259 B2 JP6065259 B2 JP 6065259B2 JP 2012197246 A JP2012197246 A JP 2012197246A JP 2012197246 A JP2012197246 A JP 2012197246A JP 6065259 B2 JP6065259 B2 JP 6065259B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- substituent
- bis
- carbon atoms
- optionally substituted
- 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.)
- Active
Links
- 150000001412 amines Chemical class 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- -1 amine compound Chemical class 0.000 claims description 169
- 125000001424 substituent group Chemical group 0.000 claims description 132
- 125000004432 carbon atom Chemical group C* 0.000 claims description 90
- 125000000217 alkyl group Chemical group 0.000 claims description 65
- 125000003118 aryl group Chemical group 0.000 claims description 48
- 125000003545 alkoxy group Chemical group 0.000 claims description 33
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 claims description 31
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims description 29
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 26
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 26
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 23
- 125000005843 halogen group Chemical group 0.000 claims description 20
- 125000002947 alkylene group Chemical group 0.000 claims description 19
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 125000005530 alkylenedioxy group Chemical group 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000012327 Ruthenium complex Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 125000005842 heteroatom Chemical group 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 8
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- 150000001721 carbon Chemical group 0.000 claims description 4
- 125000005156 substituted alkylene group Chemical group 0.000 claims description 4
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 3
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 3
- 125000005415 substituted alkoxy group Chemical group 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- QRAOZQGIUIDZQZ-UHFFFAOYSA-N 4-methyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,3-dihydro-1,4-benzoxazine Chemical class C=1C=C2N(C)CCOC2=CC=1B1OC(C)(C)C(C)(C)O1 QRAOZQGIUIDZQZ-UHFFFAOYSA-N 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 1
- 125000001567 quinoxalinyl group Chemical class N1=C(C=NC2=CC=CC=C12)* 0.000 claims 1
- 125000003107 substituted aryl group Chemical group 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 description 45
- 229910052739 hydrogen Inorganic materials 0.000 description 45
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 26
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 25
- 239000000243 solution Substances 0.000 description 21
- 229910052786 argon Inorganic materials 0.000 description 20
- 150000002431 hydrogen Chemical group 0.000 description 20
- 230000003287 optical effect Effects 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- ALHUXMDEZNLFTA-UHFFFAOYSA-N 2-methylquinoxaline Chemical compound C1=CC=CC2=NC(C)=CN=C21 ALHUXMDEZNLFTA-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 125000003277 amino group Chemical group 0.000 description 11
- 239000002585 base Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- XJJVPYMFHXMROQ-UHFFFAOYSA-N [4-[5-bis(3,5-dimethylphenyl)phosphanyl-1,3-benzodioxol-4-yl]-1,3-benzodioxol-5-yl]-bis(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(P(C=2C=C(C)C=C(C)C=2)C=2C(=C3OCOC3=CC=2)C=2C(=CC=C3OCOC3=2)P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)=C1 XJJVPYMFHXMROQ-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 150000003304 ruthenium compounds Chemical class 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 125000004122 cyclic group Chemical group 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 125000000732 arylene group Chemical group 0.000 description 8
- GPFIUEZTNRNFGD-UHFFFAOYSA-N bis(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(PC=2C=C(C)C=C(C)C=2)=C1 GPFIUEZTNRNFGD-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 125000001624 naphthyl group Chemical group 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 6
- 125000002541 furyl group Chemical group 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 150000002466 imines Chemical class 0.000 description 6
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 6
- 125000002950 monocyclic group Chemical group 0.000 description 6
- 125000006606 n-butoxy group Chemical group 0.000 description 6
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 6
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 description 6
- 125000003367 polycyclic group Chemical group 0.000 description 6
- 125000004076 pyridyl group Chemical group 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 125000001544 thienyl group Chemical group 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 238000007872 degassing Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 125000001072 heteroaryl group Chemical group 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 150000007530 organic bases Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003303 ruthenium Chemical class 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- RKJUIXBNRJVNHR-UHFFFAOYSA-N 3H-indole Chemical compound C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- BFJVWYAENGOFFP-UHFFFAOYSA-N [3-(2-diphenylphosphanyl-1-benzothiophen-3-yl)-1-benzothiophen-2-yl]-diphenylphosphane Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=C(C=2C3=CC=CC=C3SC=2P(C=2C=CC=CC=2)C=2C=CC=CC=2)C2=CC=CC=C2S1 BFJVWYAENGOFFP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000007529 inorganic bases Chemical class 0.000 description 3
- 125000005561 phenanthryl group Chemical group 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 125000000714 pyrimidinyl group Chemical group 0.000 description 3
- 150000003252 quinoxalines Chemical class 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000012552 review Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- QKZWXPLBVCKXNQ-UHFFFAOYSA-N (2-methoxyphenyl)-[2-[(2-methoxyphenyl)-phenylphosphanyl]ethyl]-phenylphosphane Chemical compound COC1=CC=CC=C1P(C=1C=CC=CC=1)CCP(C=1C(=CC=CC=1)OC)C1=CC=CC=C1 QKZWXPLBVCKXNQ-UHFFFAOYSA-N 0.000 description 2
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N 1-Pyrroline Chemical compound C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 2
- WGOBPPNNYVSJTE-UHFFFAOYSA-N 1-diphenylphosphanylpropan-2-yl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C(C)CP(C=1C=CC=CC=1)C1=CC=CC=C1 WGOBPPNNYVSJTE-UHFFFAOYSA-N 0.000 description 2
- XCYJPXQACVEIOS-UHFFFAOYSA-N 1-isopropyl-3-methylbenzene Chemical compound CC(C)C1=CC=CC(C)=C1 XCYJPXQACVEIOS-UHFFFAOYSA-N 0.000 description 2
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical compound C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- ZSOLLSAKMTZPAJ-UHFFFAOYSA-N 2,6,7-trimethylquinoxaline Chemical compound C1=C(C)C(C)=CC2=NC(C)=CN=C21 ZSOLLSAKMTZPAJ-UHFFFAOYSA-N 0.000 description 2
- AZIKLVKMNRNGPH-UHFFFAOYSA-N 2-(2-methylpropyl)quinoxaline Chemical compound C1=CC=CC2=NC(CC(C)C)=CN=C21 AZIKLVKMNRNGPH-UHFFFAOYSA-N 0.000 description 2
- TWCDSGHATZBOFX-UHFFFAOYSA-N 2-benzylquinoxaline Chemical compound C=1N=C2C=CC=CC2=NC=1CC1=CC=CC=C1 TWCDSGHATZBOFX-UHFFFAOYSA-N 0.000 description 2
- KXSIUJJLRBAPGB-UHFFFAOYSA-N 2-ethylquinoxaline Chemical compound C1=CC=CC2=NC(CC)=CN=C21 KXSIUJJLRBAPGB-UHFFFAOYSA-N 0.000 description 2
- VOJMHHWAAIBCJJ-UHFFFAOYSA-N 2-propylquinoxaline Chemical compound C1=CC=CC2=NC(CCC)=CN=C21 VOJMHHWAAIBCJJ-UHFFFAOYSA-N 0.000 description 2
- 150000005131 2H-1,4-benzoxazines Chemical class 0.000 description 2
- PVTXJGJDOHYFOX-UHFFFAOYSA-N 2h-1,4-benzoxazine Chemical compound C1=CC=C2N=CCOC2=C1 PVTXJGJDOHYFOX-UHFFFAOYSA-N 0.000 description 2
- FWXAUDSWDBGCMN-UHFFFAOYSA-N 3-diphenylphosphanylbutan-2-yl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C(C)C(C)P(C=1C=CC=CC=1)C1=CC=CC=C1 FWXAUDSWDBGCMN-UHFFFAOYSA-N 0.000 description 2
- GMSWGAOENMAHID-UHFFFAOYSA-N 3-methyl-2h-1,4-benzoxazine Chemical compound C1=CC=C2OCC(C)=NC2=C1 GMSWGAOENMAHID-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- CTYPJIUQROQJBG-UHFFFAOYSA-N 4-diphenylphosphanylpentan-2-yl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C(C)CC(C)P(C=1C=CC=CC=1)C1=CC=CC=C1 CTYPJIUQROQJBG-UHFFFAOYSA-N 0.000 description 2
- PMCYHTDCTXRDFL-UHFFFAOYSA-N 6,7-dichloro-2-methylquinoxaline Chemical compound C1=C(Cl)C(Cl)=CC2=NC(C)=CN=C21 PMCYHTDCTXRDFL-UHFFFAOYSA-N 0.000 description 2
- DJACXKBXNSFQAU-UHFFFAOYSA-N 6-chloro-2-methylquinoxaline Chemical compound C1=C(Cl)C=CC2=NC(C)=CN=C21 DJACXKBXNSFQAU-UHFFFAOYSA-N 0.000 description 2
- OCLYZMMJKAVJLU-UHFFFAOYSA-N 6-methoxy-2-methylquinoxaline Chemical compound N1=C(C)C=NC2=CC(OC)=CC=C21 OCLYZMMJKAVJLU-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- 241001120493 Arene Species 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- DGBWMTOQHQYSFD-UHFFFAOYSA-N [1-[2-bis(3,5-dimethylphenyl)phosphanyloxy-3-phenylnaphthalen-1-yl]-3-phenylnaphthalen-2-yl]oxy-bis(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(P(OC=2C(=C3C=CC=CC3=CC=2C=2C=CC=CC=2)C=2C3=CC=CC=C3C=C(C=2OP(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)C=2C=CC=CC=2)C=2C=C(C)C=C(C)C=2)=C1 DGBWMTOQHQYSFD-UHFFFAOYSA-N 0.000 description 2
- RYXZOQOZERSHHQ-UHFFFAOYSA-N [2-(2-diphenylphosphanylphenoxy)phenyl]-diphenylphosphane Chemical compound C=1C=CC=C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1OC1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RYXZOQOZERSHHQ-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- RDOWQLZANAYVLL-UHFFFAOYSA-N phenanthridine Chemical compound C1=CC=C2C3=CC=CC=C3C=NC2=C1 RDOWQLZANAYVLL-UHFFFAOYSA-N 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 125000005951 trifluoromethanesulfonyloxy group Chemical group 0.000 description 2
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 description 1
- GYKMEKRMASHMIH-UHFFFAOYSA-N (1-benzyl-4-diphenylphosphanylpyrrolidin-3-yl)-diphenylphosphane Chemical compound C=1C=CC=CC=1CN(C1)CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C1P(C=1C=CC=CC=1)C1=CC=CC=C1 GYKMEKRMASHMIH-UHFFFAOYSA-N 0.000 description 1
- IMYBACKMXRBRJW-CRBDUOJFSA-N (2r,5s)-7-[2-[(1r,2s,4r,5s)-2,5-dimethyl-7-phosphabicyclo[2.2.1]heptan-7-yl]phenyl]-2,5-dimethyl-7-phosphabicyclo[2.2.1]heptane Chemical compound P1([C@@]2([H])[C@@H](C)C[C@@]1([C@H](C2)C)[H])C1=CC=CC=C1P1C2[C@H](C)CC1[C@@H](C)C2 IMYBACKMXRBRJW-CRBDUOJFSA-N 0.000 description 1
- KOUOWTOAWJUDNH-JTQLQIEISA-N (2s)-2-(2-methylpropyl)-1,2,3,4-tetrahydroquinoxaline Chemical compound C1=CC=C2N[C@@H](CC(C)C)CNC2=C1 KOUOWTOAWJUDNH-JTQLQIEISA-N 0.000 description 1
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- CDJHPMXMJUCLPA-UHFFFAOYSA-N (3-diphenylphosphanyl-2-bicyclo[2.2.1]hept-5-enyl)-diphenylphosphane Chemical compound C1C2C=CC1C(P(C=1C=CC=CC=1)C=1C=CC=CC=1)C2P(C=1C=CC=CC=1)C1=CC=CC=C1 CDJHPMXMJUCLPA-UHFFFAOYSA-N 0.000 description 1
- BSDVKBWLRCKPFB-ZETCQYMHSA-N (3s)-3-methyl-3,4-dihydro-2h-1,4-benzoxazine Chemical compound C1=CC=C2N[C@@H](C)COC2=C1 BSDVKBWLRCKPFB-ZETCQYMHSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 1
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- LAXRNWSASWOFOT-UHFFFAOYSA-J (cymene)ruthenium dichloride dimer Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ru+2].[Ru+2].CC(C)C1=CC=C(C)C=C1.CC(C)C1=CC=C(C)C=C1 LAXRNWSASWOFOT-UHFFFAOYSA-J 0.000 description 1
- GTIXSUJKFAATAE-UHFFFAOYSA-N (r)-c3-tunephos Chemical compound C=12C(C(=CC=C3)P(C=4C=CC=CC=4)C=4C=CC=CC=4)=C3OCCCOC2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 GTIXSUJKFAATAE-UHFFFAOYSA-N 0.000 description 1
- LYHOBZAADXPPNW-UHFFFAOYSA-N (r)-xylyl-phanephos Chemical compound CC1=CC(C)=CC(P(C=2C=C(C)C=C(C)C=2)C=2C=3CCC4=CC=C(C(=C4)P(C=4C=C(C)C=C(C)C=4)C=4C=C(C)C=C(C)C=4)CCC(=CC=3)C=2)=C1 LYHOBZAADXPPNW-UHFFFAOYSA-N 0.000 description 1
- AEBHGEORFJJOMI-UHFFFAOYSA-N 1,1-bis(3-methoxyphenyl)-3-methylbutane-1,2-diamine Chemical compound COC1=CC=CC(C(N)(C(N)C(C)C)C=2C=C(OC)C=CC=2)=C1 AEBHGEORFJJOMI-UHFFFAOYSA-N 0.000 description 1
- WDYGPMAMBXJESZ-UHFFFAOYSA-N 1,1-bis(4-methoxyphenyl)-3-methylbutane-1,2-diamine Chemical compound C1=CC(OC)=CC=C1C(N)(C(N)C(C)C)C1=CC=C(OC)C=C1 WDYGPMAMBXJESZ-UHFFFAOYSA-N 0.000 description 1
- RYEKIQZUTHKUKD-UHFFFAOYSA-N 1,1-bis(4-methoxyphenyl)-4-methylpentane-1,2-diamine Chemical compound C1=CC(OC)=CC=C1C(N)(C(N)CC(C)C)C1=CC=C(OC)C=C1 RYEKIQZUTHKUKD-UHFFFAOYSA-N 0.000 description 1
- FUIAQGXJJSEAJH-UHFFFAOYSA-N 1,1-bis(4-methoxyphenyl)propane-1,2-diamine Chemical compound C1=CC(OC)=CC=C1C(N)(C(C)N)C1=CC=C(OC)C=C1 FUIAQGXJJSEAJH-UHFFFAOYSA-N 0.000 description 1
- OWUQWDCZCOJEKU-UHFFFAOYSA-N 1,1-diphenylpropane-1,2-diamine Chemical compound C=1C=CC=CC=1C(N)(C(N)C)C1=CC=CC=C1 OWUQWDCZCOJEKU-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- ZWMPRHYHRAUVGY-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethane-1,2-diamine Chemical compound C1=CC(OC)=CC=C1C(N)C(N)C1=CC=C(OC)C=C1 ZWMPRHYHRAUVGY-UHFFFAOYSA-N 0.000 description 1
- PONXTPCRRASWKW-UHFFFAOYSA-N 1,2-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1C(N)C(N)C1=CC=CC=C1 PONXTPCRRASWKW-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- FVIRPXURSWZMSH-UHFFFAOYSA-N 1,3-dimethylideneguanidine Chemical compound C=NC(=N)N=C FVIRPXURSWZMSH-UHFFFAOYSA-N 0.000 description 1
- VPKAHUMPZYVNIV-UHFFFAOYSA-N 1,4-dihydroisoquinoline Chemical compound C1=CC=C2CC=NCC2=C1 VPKAHUMPZYVNIV-UHFFFAOYSA-N 0.000 description 1
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 1
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical compound N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 description 1
- DBFOTDPGDNMJDQ-UHFFFAOYSA-N 1-(2-aminonaphthalen-1-yl)-3-bis(3,5-dimethylphenyl)phosphanylnaphthalen-2-amine Chemical compound C1(=CC(=CC(=C1)C)C)P(C1=CC(=CC(=C1)C)C)C1=C(C(=C2C=CC=CC2=C1)C=1C(=CC=C2C=CC=CC=12)N)N DBFOTDPGDNMJDQ-UHFFFAOYSA-N 0.000 description 1
- ULQKSXBJWWNCRY-UHFFFAOYSA-N 1-(2-aminonaphthalen-1-yl)-3-diphenylphosphanylnaphthalen-2-amine Chemical compound C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=C(C(=C2C=CC=CC2=C1)C=1C(=CC=C2C=CC=CC=12)N)N ULQKSXBJWWNCRY-UHFFFAOYSA-N 0.000 description 1
- WWRCMNKATXZARA-UHFFFAOYSA-N 1-Isopropyl-2-methylbenzene Chemical compound CC(C)C1=CC=CC=C1C WWRCMNKATXZARA-UHFFFAOYSA-N 0.000 description 1
- QGOJLFDHRRRRHP-UHFFFAOYSA-N 1-[2-(2,4-dimethylphosphetan-1-yl)ethyl]-2,4-dimethylphosphetane Chemical compound CC1CC(C)P1CCP1C(C)CC1C QGOJLFDHRRRRHP-UHFFFAOYSA-N 0.000 description 1
- IXYQOQUDOYFALZ-UHFFFAOYSA-N 1-[2-(2,4-dimethylphosphetan-1-yl)phenyl]-2,4-dimethylphosphetane Chemical compound CC1CC(C)P1C1=CC=CC=C1P1C(C)CC1C IXYQOQUDOYFALZ-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 1
- DWKUKQRKVCMOLP-UHFFFAOYSA-N 1-piperideine Chemical compound C1CCN=CC1 DWKUKQRKVCMOLP-UHFFFAOYSA-N 0.000 description 1
- SJNUZTRUIDRSJK-UHFFFAOYSA-N 1-tert-butyl-2-(1-tert-butylphospholan-2-yl)phospholane Chemical compound CC(C)(C)P1CCCC1C1P(C(C)(C)C)CCC1 SJNUZTRUIDRSJK-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- ZBONBGOYILUGCL-UHFFFAOYSA-N 2,2-dimethylpropanoate Chemical compound CC(C)([CH2+])C([O-])=O ZBONBGOYILUGCL-UHFFFAOYSA-N 0.000 description 1
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- GNMWFZWAAAJPLO-UHFFFAOYSA-N 2,4-diethylphosphetane Chemical group CCC1CC(CC)P1 GNMWFZWAAAJPLO-UHFFFAOYSA-N 0.000 description 1
- WDSCSGNNYCRSBO-UHFFFAOYSA-N 2,4-dimethylphosphetane Chemical group CC1CC(C)P1 WDSCSGNNYCRSBO-UHFFFAOYSA-N 0.000 description 1
- WXCZOPWVRGQMKE-UHFFFAOYSA-N 2,6,7-trimethyl-1,2,3,4-tetrahydroquinoxaline Chemical compound CC1=C(C)C=C2NC(C)CNC2=C1 WXCZOPWVRGQMKE-UHFFFAOYSA-N 0.000 description 1
- KMOUOJXSBJDDKH-UHFFFAOYSA-N 2-(3,4-dimethyl-1-phenyl-2,5-dihydrophosphol-2-yl)-3,4-dimethyl-1-phenyl-2,5-dihydrophosphole Chemical compound C=1C=CC=CC=1P1CC(C)=C(C)C1C(C(=C(C)C1)C)P1C1=CC=CC=C1 KMOUOJXSBJDDKH-UHFFFAOYSA-N 0.000 description 1
- WKFXZVGNWUGIPO-UHFFFAOYSA-N 2-[2-[2-(1-diphenylphosphanyloxy-2-methyl-1-oxopropan-2-yl)phenyl]phenyl]-2-methylpropanoic acid Chemical compound CC(C)(C(O)=O)C(C=CC=C1)=C1C1=C(C(C)(C)C(OP(C2=CC=CC=C2)C2=CC=CC=C2)=O)C=CC=C1 WKFXZVGNWUGIPO-UHFFFAOYSA-N 0.000 description 1
- YNHLICIGPDDDNF-UHFFFAOYSA-N 2-bis(3,5-dimethylphenyl)phosphanyl-3-[2-bis(3,5-dimethylphenyl)phosphanyl-3-hydroxy-6-methoxyphenyl]-4-methoxyphenol Chemical compound COC=1C=CC(O)=C(P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)C=1C=1C(OC)=CC=C(O)C=1P(C=1C=C(C)C=C(C)C=1)C1=CC(C)=CC(C)=C1 YNHLICIGPDDDNF-UHFFFAOYSA-N 0.000 description 1
- HOGDYFQNKKWTEK-UHFFFAOYSA-N 2-diphenylphosphanyl-3-(2-diphenylphosphanyl-3-hydroxy-6-methoxyphenyl)-4-methoxyphenol Chemical compound COC=1C=CC(O)=C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1C=1C(OC)=CC=C(O)C=1P(C=1C=CC=CC=1)C1=CC=CC=C1 HOGDYFQNKKWTEK-UHFFFAOYSA-N 0.000 description 1
- PFGRBAYSEQEFQN-UHFFFAOYSA-N 2-methyl-1,2,3,4-tetrahydroquinoxaline Chemical compound C1=CC=C2NC(C)CNC2=C1 PFGRBAYSEQEFQN-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- FQBFZYRWDRXSDM-UHFFFAOYSA-N 2H-1,5-dioxonine Chemical compound O1CC=COC=CC=C1 FQBFZYRWDRXSDM-UHFFFAOYSA-N 0.000 description 1
- VHMICKWLTGFITH-UHFFFAOYSA-N 2H-isoindole Chemical compound C1=CC=CC2=CNC=C21 VHMICKWLTGFITH-UHFFFAOYSA-N 0.000 description 1
- JZIBVTUXIVIFGC-UHFFFAOYSA-N 2H-pyrrole Chemical compound C1C=CC=N1 JZIBVTUXIVIFGC-UHFFFAOYSA-N 0.000 description 1
- ACVSHQGHCWUJFU-UHFFFAOYSA-N 2h-imidazole Chemical compound C1N=CC=N1 ACVSHQGHCWUJFU-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- DNNVRTZJRKIUFK-UHFFFAOYSA-N 3,4-dihydroquinoline Chemical compound C1=CC=C2N=CCCC2=C1 DNNVRTZJRKIUFK-UHFFFAOYSA-N 0.000 description 1
- UYRXWZGOHPWMIZ-UHFFFAOYSA-N 3-[2-[2-(3-diphenylphosphanyloxy-2,2-dimethyl-3-oxopropyl)phenyl]phenyl]-2,2-dimethylpropanoic acid Chemical compound CC(C)(CC(C=CC=C1)=C1C1=C(CC(C)(C)C(OP(C2=CC=CC=C2)C2=CC=CC=C2)=O)C=CC=C1)C(O)=O UYRXWZGOHPWMIZ-UHFFFAOYSA-N 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 1
- UGYCWJKLMOREKO-UHFFFAOYSA-N 3-methyl-1,1-diphenylbutane-1,2-diamine Chemical compound C=1C=CC=CC=1C(N)(C(N)C(C)C)C1=CC=CC=C1 UGYCWJKLMOREKO-UHFFFAOYSA-N 0.000 description 1
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- PEXFGZJGEXXSBE-UHFFFAOYSA-N 4-methyl-1,1-diphenylpentane-1,2-diamine Chemical compound C=1C=CC=CC=1C(N)(C(N)CC(C)C)C1=CC=CC=C1 PEXFGZJGEXXSBE-UHFFFAOYSA-N 0.000 description 1
- KIXFHDAJQHFSPD-UHFFFAOYSA-N 6,7-dichloro-2-methyl-1,2,3,4-tetrahydroquinoxaline Chemical compound ClC1=C(Cl)C=C2NC(C)CNC2=C1 KIXFHDAJQHFSPD-UHFFFAOYSA-N 0.000 description 1
- KETYISNANWDTPX-UHFFFAOYSA-N 6-chloro-2-methyl-1,2,3,4-tetrahydroquinoxaline Chemical compound ClC1=CC=C2NC(C)CNC2=C1 KETYISNANWDTPX-UHFFFAOYSA-N 0.000 description 1
- ABWRTJOSJMFSFD-UHFFFAOYSA-N 6-methoxy-2-methyl-1,2,3,4-tetrahydroquinoxaline Chemical compound N1C(C)CNC2=CC(OC)=CC=C21 ABWRTJOSJMFSFD-UHFFFAOYSA-N 0.000 description 1
- VBRHAEBNGYPNKI-UHFFFAOYSA-N C1(=CC(=CC(=C1)C)C)P(C1=CC(=CC(=C1)C)C)C1OC2=C(C1)C=CC=C2C2=CC=CC=1CCOC12 Chemical compound C1(=CC(=CC(=C1)C)C)P(C1=CC(=CC(=C1)C)C)C1OC2=C(C1)C=CC=C2C2=CC=CC=1CCOC12 VBRHAEBNGYPNKI-UHFFFAOYSA-N 0.000 description 1
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 1
- UIQCFIIULQJLAI-UHFFFAOYSA-N C1OC(C2=CC=CC=C2C=C2)=C2C1=C1C2=CC=C3C=CC=CC3=C2OC1(P(C=1C=CC=CC=1)C=1C=CC=CC=1)P(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound C1OC(C2=CC=CC=C2C=C2)=C2C1=C1C2=CC=C3C=CC=CC3=C2OC1(P(C=1C=CC=CC=1)C=1C=CC=CC=1)P(C=1C=CC=CC=1)C1=CC=CC=C1 UIQCFIIULQJLAI-UHFFFAOYSA-N 0.000 description 1
- 125000005915 C6-C14 aryl group Chemical group 0.000 description 1
- XYHPQNWJKYWQMI-UHFFFAOYSA-N CC(C)(CC(C=C1C(C(OC)=CC=C2CC(C)(C)C(O)=O)=C2P(C2=CC(C)=CC(C)=C2)C2=CC(C)=CC(C)=C2)=CC=C1OC)C(O)=O Chemical compound CC(C)(CC(C=C1C(C(OC)=CC=C2CC(C)(C)C(O)=O)=C2P(C2=CC(C)=CC(C)=C2)C2=CC(C)=CC(C)=C2)=CC=C1OC)C(O)=O XYHPQNWJKYWQMI-UHFFFAOYSA-N 0.000 description 1
- OKSDMIAODZKBGY-UHFFFAOYSA-N COC=1C=CC(CC(C)(C)C(O)=O)=C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1C=1C(OC)=CC=C(CC(C)(C)C(O)=O)C=1P(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound COC=1C=CC(CC(C)(C)C(O)=O)=C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1C=1C(OC)=CC=C(CC(C)(C)C(O)=O)C=1P(C=1C=CC=CC=1)C1=CC=CC=C1 OKSDMIAODZKBGY-UHFFFAOYSA-N 0.000 description 1
- NPKDQTXYJNEDNH-UHFFFAOYSA-N C[PH3]C1=CC=C(C=C1)[PH3]C Chemical compound C[PH3]C1=CC=C(C=C1)[PH3]C NPKDQTXYJNEDNH-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- OPWYAUGTRDDDOH-UHFFFAOYSA-N [1-(2-diphenylphosphanylbenzimidazol-1-yl)benzimidazol-2-yl]-diphenylphosphane Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=NC2=CC=CC=C2N1N1C2=CC=CC=C2N=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 OPWYAUGTRDDDOH-UHFFFAOYSA-N 0.000 description 1
- JZJPYBVTTOSAOG-UHFFFAOYSA-N [1-(2-diphenylphosphanyloxynaphthalen-1-yl)naphthalen-2-yl]oxy-diphenylphosphane Chemical group C=1C=C2C=CC=CC2=C(C=2C3=CC=CC=C3C=CC=2OP(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1OP(C=1C=CC=CC=1)C1=CC=CC=C1 JZJPYBVTTOSAOG-UHFFFAOYSA-N 0.000 description 1
- QJMWBZZIWFLBLM-UHFFFAOYSA-N [1-[2-bis(3,5-dimethylphenyl)phosphanyl-4-bromonaphthalen-1-yl]-4-bromonaphthalen-2-yl]-bis(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(P(C=2C=C(C)C=C(C)C=2)C=2C(=C3C=CC=CC3=C(Br)C=2)C=2C3=CC=CC=C3C(Br)=CC=2P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)=C1 QJMWBZZIWFLBLM-UHFFFAOYSA-N 0.000 description 1
- NXCDNNJNHGMINO-UHFFFAOYSA-N [1-[2-bis(3,5-dimethylphenyl)phosphanyl-4-chloronaphthalen-1-yl]-4-chloronaphthalen-2-yl]-bis(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(P(C=2C=C(C)C=C(C)C=2)C=2C(=C3C=CC=CC3=C(Cl)C=2)C=2C3=CC=CC=C3C(Cl)=CC=2P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)=C1 NXCDNNJNHGMINO-UHFFFAOYSA-N 0.000 description 1
- PREOAGGLTJMIJA-UHFFFAOYSA-N [1-[2-bis(3,5-dimethylphenyl)phosphanyl-4-methylnaphthalen-1-yl]-4-methylnaphthalen-2-yl]-bis(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(P(C=2C=C(C)C=C(C)C=2)C=2C(=C3C=CC=CC3=C(C)C=2)C=2C3=CC=CC=C3C(C)=CC=2P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)=C1 PREOAGGLTJMIJA-UHFFFAOYSA-N 0.000 description 1
- FGZOOFIFTNRDLF-UHFFFAOYSA-N [1-[2-bis(3,5-dimethylphenyl)phosphanyl-4-tri(propan-2-yl)silylnaphthalen-1-yl]-4-tri(propan-2-yl)silylnaphthalen-2-yl]-bis(3,5-dimethylphenyl)phosphane Chemical compound C=1C(C)=CC(C)=CC=1P(C=1C=C(C)C=C(C)C=1)C=1C=C([Si](C(C)C)(C(C)C)C(C)C)C2=CC=CC=C2C=1C=1C2=CC=CC=C2C([Si](C(C)C)(C(C)C)C(C)C)=CC=1P(C=1C=C(C)C=C(C)C=1)C1=CC(C)=CC(C)=C1 FGZOOFIFTNRDLF-UHFFFAOYSA-N 0.000 description 1
- HKJQBXZQTMJPEN-UHFFFAOYSA-N [1-[2-bis(3,5-dimethylphenyl)phosphanyl-4-trimethylsilylnaphthalen-1-yl]-4-trimethylsilylnaphthalen-2-yl]-bis(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(P(C=2C=C(C)C=C(C)C=2)C=2C(=C3C=CC=CC3=C(C=2)[Si](C)(C)C)C=2C3=CC=CC=C3C(=CC=2P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)[Si](C)(C)C)=C1 HKJQBXZQTMJPEN-UHFFFAOYSA-N 0.000 description 1
- CZZUTGFLNZVSDN-UHFFFAOYSA-N [1-[2-bis(3,5-dimethylphenyl)phosphanyl-6-[tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silyl]naphthalen-1-yl]-6-[tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silyl]naphthalen-2-yl]-bis(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(P(C=2C=C(C)C=C(C)C=2)C=2C(=C3C=CC(=CC3=CC=2)[Si](CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)(CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C=2C3=CC=C(C=C3C=CC=2P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)[Si](CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)(CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)=C1 CZZUTGFLNZVSDN-UHFFFAOYSA-N 0.000 description 1
- QRXUBGVJGGCOMA-UHFFFAOYSA-N [1-[2-bis(3,5-dimethylphenyl)phosphanyl-7-methoxynaphthalen-1-yl]-7-methoxynaphthalen-2-yl]-bis(3,5-dimethylphenyl)phosphane Chemical compound C=1C(C)=CC(C)=CC=1P(C=1C=C(C)C=C(C)C=1)C=1C=CC2=CC=C(OC)C=C2C=1C=1C2=CC(OC)=CC=C2C=CC=1P(C=1C=C(C)C=C(C)C=1)C1=CC(C)=CC(C)=C1 QRXUBGVJGGCOMA-UHFFFAOYSA-N 0.000 description 1
- MXGXXBYVDMVJAO-UHFFFAOYSA-N [1-[2-bis(3,5-dimethylphenyl)phosphanylnaphthalen-1-yl]naphthalen-2-yl]-bis(3,5-dimethylphenyl)phosphane Chemical group CC1=CC(C)=CC(P(C=2C=C(C)C=C(C)C=2)C=2C(=C3C=CC=CC3=CC=2)C=2C3=CC=CC=C3C=CC=2P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)=C1 MXGXXBYVDMVJAO-UHFFFAOYSA-N 0.000 description 1
- BCNYNKKGQKMGES-UHFFFAOYSA-N [1-[2-bis(3,5-dimethylphenyl)phosphanyloxy-3-methylnaphthalen-1-yl]-3-methylnaphthalen-2-yl]oxy-bis(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(P(OC=2C(=C3C=CC=CC3=CC=2C)C=2C3=CC=CC=C3C=C(C)C=2OP(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)=C1 BCNYNKKGQKMGES-UHFFFAOYSA-N 0.000 description 1
- CRELPJJGSLSRBO-UHFFFAOYSA-N [1-[2-bis(3,5-ditert-butyl-4-methoxyphenyl)phosphanylnaphthalen-1-yl]naphthalen-2-yl]-bis(3,5-ditert-butyl-4-methoxyphenyl)phosphane Chemical group C1=C(C(C)(C)C)C(OC)=C(C(C)(C)C)C=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=C(C(OC)=C(C=1)C(C)(C)C)C(C)(C)C)C=1C=C(C(OC)=C(C=1)C(C)(C)C)C(C)(C)C)C1=CC(C(C)(C)C)=C(OC)C(C(C)(C)C)=C1 CRELPJJGSLSRBO-UHFFFAOYSA-N 0.000 description 1
- ZXLSIBHBPGQKLI-UHFFFAOYSA-N [1-[2-bis(3-methylphenyl)phosphanyl-5,6,7,8-tetrahydronaphthalen-1-yl]-5,6,7,8-tetrahydronaphthalen-2-yl]-bis(3-methylphenyl)phosphane Chemical group CC1=CC=CC(P(C=2C=C(C)C=CC=2)C=2C(=C3CCCCC3=CC=2)C=2C=3CCCCC=3C=CC=2P(C=2C=C(C)C=CC=2)C=2C=C(C)C=CC=2)=C1 ZXLSIBHBPGQKLI-UHFFFAOYSA-N 0.000 description 1
- MJRVUGAHDHEPEL-UHFFFAOYSA-N [1-[2-bis(3-methylphenyl)phosphanylnaphthalen-1-yl]naphthalen-2-yl]-bis(3-methylphenyl)phosphane Chemical group CC1=CC=CC(P(C=2C=C(C)C=CC=2)C=2C(=C3C=CC=CC3=CC=2)C=2C3=CC=CC=C3C=CC=2P(C=2C=C(C)C=CC=2)C=2C=C(C)C=CC=2)=C1 MJRVUGAHDHEPEL-UHFFFAOYSA-N 0.000 description 1
- VEYRFPIBBZGJTR-UHFFFAOYSA-N [1-[2-bis(4-methoxyphenyl)phosphanylnaphthalen-1-yl]naphthalen-2-yl]-bis(4-methoxyphenyl)phosphane Chemical group C1=CC(OC)=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 VEYRFPIBBZGJTR-UHFFFAOYSA-N 0.000 description 1
- LPIWZWWQDQFJAT-UHFFFAOYSA-N [1-[2-bis(4-methylphenyl)phosphanyl-5,6,7,8-tetrahydronaphthalen-1-yl]-5,6,7,8-tetrahydronaphthalen-2-yl]-bis(4-methylphenyl)phosphane Chemical group C1=CC(C)=CC=C1P(C=1C(=C2CCCCC2=CC=1)C=1C=2CCCCC=2C=CC=1P(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 LPIWZWWQDQFJAT-UHFFFAOYSA-N 0.000 description 1
- IOPQYDKQISFMJI-UHFFFAOYSA-N [1-[2-bis(4-methylphenyl)phosphanylnaphthalen-1-yl]naphthalen-2-yl]-bis(4-methylphenyl)phosphane Chemical group C1=CC(C)=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 IOPQYDKQISFMJI-UHFFFAOYSA-N 0.000 description 1
- TWQOFLZNCSPELF-UHFFFAOYSA-N [2-(1-diphenylphosphanyl-3-methylindol-2-yl)-3-methylindol-1-yl]-diphenylphosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)N1C2=CC=CC=C2C(C)=C1C1=C(C)C2=CC=CC=C2N1P(C=1C=CC=CC=1)C1=CC=CC=C1 TWQOFLZNCSPELF-UHFFFAOYSA-N 0.000 description 1
- AXEUQWSHUARFGH-UHFFFAOYSA-N [2-(2-acetyloxyphenyl)phenyl] acetate Chemical compound CC(=O)OC1=CC=CC=C1C1=CC=CC=C1OC(C)=O AXEUQWSHUARFGH-UHFFFAOYSA-N 0.000 description 1
- ZVGIMWNAJMKRHI-UHFFFAOYSA-N [2-(2-diphenylphosphanyl-6-methoxy-3-propan-2-ylphenyl)-3-methoxy-6-propan-2-ylphenyl]-diphenylphosphane Chemical compound COC=1C=CC(C(C)C)=C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1C=1C(OC)=CC=C(C(C)C)C=1P(C=1C=CC=CC=1)C1=CC=CC=C1 ZVGIMWNAJMKRHI-UHFFFAOYSA-N 0.000 description 1
- KRJVQCZJJSUHHO-UHFFFAOYSA-N [2-(2-diphenylphosphanyl-6-methoxyphenyl)-3-methoxyphenyl]-diphenylphosphane Chemical group COC=1C=CC=C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1C=1C(OC)=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 KRJVQCZJJSUHHO-UHFFFAOYSA-N 0.000 description 1
- WHLQQRGHOPIIMQ-UHFFFAOYSA-N [2-(2-diphenylphosphanyl-6-methylphenyl)-3-methylphenyl]-diphenylphosphane Chemical group CC=1C=CC=C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1C=1C(C)=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 WHLQQRGHOPIIMQ-UHFFFAOYSA-N 0.000 description 1
- IYTHLSFAUKKSGJ-UHFFFAOYSA-N [2-(6-diphenylphosphanyl-2,3,4-trimethoxyphenyl)-3,4,5-trimethoxyphenyl]-diphenylphosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C=1C=C(OC)C(OC)=C(OC)C=1C=1C(OC)=C(OC)C(OC)=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 IYTHLSFAUKKSGJ-UHFFFAOYSA-N 0.000 description 1
- SLDQCQKPWTZBAG-UHFFFAOYSA-N [2-[2-bis(3,5-dimethylphenyl)phosphanyl-4,6-bis(trifluoromethyl)phenyl]-4-methoxy-3,5-dimethylphenyl]-bis(3,5-dimethylphenyl)phosphane Chemical compound C=1C(C)=CC(C)=CC=1P(C=1C=C(C)C=C(C)C=1)C=1C=C(C(F)(F)F)C=C(C(F)(F)F)C=1C1=C(C)C(OC)=C(C)C=C1P(C=1C=C(C)C=C(C)C=1)C1=CC(C)=CC(C)=C1 SLDQCQKPWTZBAG-UHFFFAOYSA-N 0.000 description 1
- IGJQZTKUXZOIRB-UHFFFAOYSA-N [2-[2-bis(3,5-dimethylphenyl)phosphanyl-6-methoxy-3-(4-methylphenoxy)phenyl]-3-methoxy-6-(4-methylphenoxy)phenyl]-bis(3,5-dimethylphenyl)phosphane Chemical compound C=1C(C)=CC(C)=CC=1P(C=1C=C(C)C=C(C)C=1)C1=C(C=2C(=C(OC=3C=CC(C)=CC=3)C=CC=2OC)P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)C(OC)=CC=C1OC1=CC=C(C)C=C1 IGJQZTKUXZOIRB-UHFFFAOYSA-N 0.000 description 1
- CXWMIUQKLNIXSL-UHFFFAOYSA-N [2-[2-bis(3,5-dimethylphenyl)phosphanyl-6-methoxy-3-propan-2-ylphenyl]-3-methoxy-6-propan-2-ylphenyl]-bis(3,5-dimethylphenyl)phosphane Chemical compound COC=1C=CC(C(C)C)=C(P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)C=1C=1C(OC)=CC=C(C(C)C)C=1P(C=1C=C(C)C=C(C)C=1)C1=CC(C)=CC(C)=C1 CXWMIUQKLNIXSL-UHFFFAOYSA-N 0.000 description 1
- IMUHNRWTDUVXOU-UHFFFAOYSA-N [2-[2-bis(3,5-dimethylphenyl)phosphanyl-6-methoxyphenyl]-3-methoxyphenyl]-bis(3,5-dimethylphenyl)phosphane Chemical group COC=1C=CC=C(P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)C=1C=1C(OC)=CC=CC=1P(C=1C=C(C)C=C(C)C=1)C1=CC(C)=CC(C)=C1 IMUHNRWTDUVXOU-UHFFFAOYSA-N 0.000 description 1
- DTMVLPFJTUJZAY-UHFFFAOYSA-N [2-[2-bis(4-methylphenyl)phosphanyl-6-methoxyphenyl]-3-methoxyphenyl]-bis(4-methylphenyl)phosphane Chemical group COC=1C=CC=C(P(C=2C=CC(C)=CC=2)C=2C=CC(C)=CC=2)C=1C=1C(OC)=CC=CC=1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 DTMVLPFJTUJZAY-UHFFFAOYSA-N 0.000 description 1
- GHUNCMLPKZAPJK-UHFFFAOYSA-N [2-[2-bis(4-methylphenyl)phosphanyl-6-methylphenyl]-3-methylphenyl]-bis(4-methylphenyl)phosphane Chemical group C1=CC(C)=CC=C1P(C=1C(=C(C)C=CC=1)C=1C(=CC=CC=1C)P(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 GHUNCMLPKZAPJK-UHFFFAOYSA-N 0.000 description 1
- KQPQCSZHVNGZIX-UHFFFAOYSA-N [2-[6-bis(3,5-dimethylphenyl)phosphanyl-2,3,4-trimethoxyphenyl]-3,4,5-trimethoxyphenyl]-bis(3,5-dimethylphenyl)phosphane Chemical compound C=1C(C)=CC(C)=CC=1P(C=1C=C(C)C=C(C)C=1)C=1C=C(OC)C(OC)=C(OC)C=1C=1C(OC)=C(OC)C(OC)=CC=1P(C=1C=C(C)C=C(C)C=1)C1=CC(C)=CC(C)=C1 KQPQCSZHVNGZIX-UHFFFAOYSA-N 0.000 description 1
- GMTUXLIGQRLFJT-UHFFFAOYSA-N [2-[6-bis(3,5-dimethylphenyl)phosphanyl-3-chloro-2,4-dimethylphenyl]-4-chloro-3,5-dimethylphenyl]-bis(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(P(C=2C=C(C)C=C(C)C=2)C=2C(=C(C)C(Cl)=C(C)C=2)C=2C(=CC(C)=C(Cl)C=2C)P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)=C1 GMTUXLIGQRLFJT-UHFFFAOYSA-N 0.000 description 1
- NLQHZRVZNIXZAU-UHFFFAOYSA-N [2-[6-bis(3,5-dimethylphenyl)phosphanyl-3-chloro-2-methoxyphenyl]-4-chloro-3-methoxyphenyl]-bis(3,5-dimethylphenyl)phosphane Chemical compound COC=1C(Cl)=CC=C(P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)C=1C=1C(OC)=C(Cl)C=CC=1P(C=1C=C(C)C=C(C)C=1)C1=CC(C)=CC(C)=C1 NLQHZRVZNIXZAU-UHFFFAOYSA-N 0.000 description 1
- NUWYAYHPAQOFGV-UHFFFAOYSA-N [2-[6-bis(3,5-dimethylphenyl)phosphanyl-3-methoxy-2,4-dimethylphenyl]-4-methoxy-3,5-dimethylphenyl]-bis(3,5-dimethylphenyl)phosphane Chemical compound CC=1C(OC)=C(C)C=C(P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)C=1C1=C(C)C(OC)=C(C)C=C1P(C=1C=C(C)C=C(C)C=1)C1=CC(C)=CC(C)=C1 NUWYAYHPAQOFGV-UHFFFAOYSA-N 0.000 description 1
- VCQUNTQMYXUAEZ-UHFFFAOYSA-N [3-(2-diphenylphosphanyl-1-benzofuran-3-yl)-1-benzofuran-2-yl]-diphenylphosphane Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=C(C=2C3=CC=CC=C3OC=2P(C=2C=CC=CC=2)C=2C=CC=CC=2)C2=CC=CC=C2O1 VCQUNTQMYXUAEZ-UHFFFAOYSA-N 0.000 description 1
- BBDULLKCXYRWHG-UHFFFAOYSA-N [3-(2-diphenylphosphanyl-4,6-dimethyl-1-benzothiophen-3-yl)-4,6-dimethyl-1-benzothiophen-2-yl]-diphenylphosphane Chemical compound S1C2=CC(C)=CC(C)=C2C(C=2C3=C(C)C=C(C)C=C3SC=2P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 BBDULLKCXYRWHG-UHFFFAOYSA-N 0.000 description 1
- MCXGLTSKWVCSMB-UHFFFAOYSA-N [3-[4-bis(2-methylphenyl)phosphanyl-2,6-dimethoxypyridin-3-yl]-2,6-dimethoxypyridin-4-yl]-bis(2-methylphenyl)phosphane Chemical compound COC=1N=C(OC)C=C(P(C=2C(=CC=CC=2)C)C=2C(=CC=CC=2)C)C=1C=1C(OC)=NC(OC)=CC=1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C MCXGLTSKWVCSMB-UHFFFAOYSA-N 0.000 description 1
- JRTHAKOHBMETRC-UHFFFAOYSA-N [3-[4-bis(3,5-dimethylphenyl)phosphanyl-2,6-dimethoxypyridin-3-yl]-2,6-dimethoxypyridin-4-yl]-bis(3,5-dimethylphenyl)phosphane Chemical compound COC=1N=C(OC)C=C(P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)C=1C=1C(OC)=NC(OC)=CC=1P(C=1C=C(C)C=C(C)C=1)C1=CC(C)=CC(C)=C1 JRTHAKOHBMETRC-UHFFFAOYSA-N 0.000 description 1
- OUKLQJWYPXWMJM-UHFFFAOYSA-N [4-(3-diphenylphosphanylphenanthren-4-yl)phenanthren-3-yl]-diphenylphosphane Chemical compound C1=CC=CC=C1P(C=1C(=C2C3=CC=CC=C3C=CC2=CC=1)C=1C2=C3C=CC=CC3=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 OUKLQJWYPXWMJM-UHFFFAOYSA-N 0.000 description 1
- YFPMTHRDOXOERU-UHFFFAOYSA-N [4-(4-diphenylphosphanyl-2,5-dimethylthiophen-3-yl)-2,5-dimethylthiophen-3-yl]-diphenylphosphane Chemical compound CC=1SC(C)=C(C=2C(=C(C)SC=2C)P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1P(C=1C=CC=CC=1)C1=CC=CC=C1 YFPMTHRDOXOERU-UHFFFAOYSA-N 0.000 description 1
- JDIOQKVMANUPKV-UHFFFAOYSA-N [4-[3-bis(3,5-dimethylphenyl)phosphanylphenanthren-4-yl]phenanthren-3-yl]-bis(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(P(C=2C=C(C)C=C(C)C=2)C=2C(=C3C4=CC=CC=C4C=CC3=CC=2)C=2C3=C4C=CC=CC4=CC=C3C=CC=2P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)=C1 JDIOQKVMANUPKV-UHFFFAOYSA-N 0.000 description 1
- KJTIJIHUORJAMV-UHFFFAOYSA-N [4-[4-(aminomethyl)-2-diphenylphosphanylnaphthalen-1-yl]-3-diphenylphosphanylnaphthalen-1-yl]methanamine;hydron;bromide Chemical compound [H+].[Br-].C=1C=CC=CC=1P(C=1C=CC=CC=1)C=1C=C(CN)C2=CC=CC=C2C=1C=1C2=CC=CC=C2C(CN)=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 KJTIJIHUORJAMV-UHFFFAOYSA-N 0.000 description 1
- ZGMYWPKVPPTZRR-UHFFFAOYSA-N [4-[5-bis(3,5-dimethylphenyl)phosphanyl-2,2-difluoro-1,3-benzodioxol-4-yl]-2,2-difluoro-1,3-benzodioxol-5-yl]-bis(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(P(C=2C=C(C)C=C(C)C=2)C=2C(=C3OC(F)(F)OC3=CC=2)C=2C(=CC=C3OC(F)(F)OC3=2)P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)=C1 ZGMYWPKVPPTZRR-UHFFFAOYSA-N 0.000 description 1
- VDAONPCHIKMLFE-UHFFFAOYSA-N [4-[5-bis(3,5-dimethylphenyl)phosphanyl-2,2-dimethyl-1,3-benzodioxol-4-yl]-2,2-dimethyl-1,3-benzodioxol-5-yl]-bis(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(P(C=2C=C(C)C=C(C)C=2)C=2C(=C3OC(C)(C)OC3=CC=2)C=2C(=CC=C3OC(C)(C)OC3=2)P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)=C1 VDAONPCHIKMLFE-UHFFFAOYSA-N 0.000 description 1
- SDXSBPIDOQBRBU-UHFFFAOYSA-N [4-chloro-1-(4-chloro-2-diphenylphosphanylnaphthalen-1-yl)naphthalen-2-yl]-diphenylphosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C=1C=C(Cl)C2=CC=CC=C2C=1C=1C2=CC=CC=C2C(Cl)=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 SDXSBPIDOQBRBU-UHFFFAOYSA-N 0.000 description 1
- HNGDFJKDVGCPGH-UHFFFAOYSA-N [4-chloro-2-(3-chloro-6-diphenylphosphanyl-2,4-dimethylphenyl)-3,5-dimethylphenyl]-diphenylphosphane Chemical compound CC=1C(Cl)=C(C)C=C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1C=1C(C)=C(Cl)C(C)=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 HNGDFJKDVGCPGH-UHFFFAOYSA-N 0.000 description 1
- VCHDBLPQYJAQSQ-UHFFFAOYSA-N [5-(diphenylphosphanylmethyl)-2,2-dimethyl-1,3-dioxolan-4-yl]methyl-diphenylphosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CC1OC(C)(C)OC1CP(C=1C=CC=CC=1)C1=CC=CC=C1 VCHDBLPQYJAQSQ-UHFFFAOYSA-N 0.000 description 1
- ODEFOLDKAQTMMX-UHFFFAOYSA-N [5-[6-bis(3,5-dimethylphenyl)phosphanyl-2,3-dihydro-1,4-benzodioxin-5-yl]-2,3-dihydro-1,4-benzodioxin-6-yl]-bis(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(P(C=2C=C(C)C=C(C)C=2)C=2C(=C3OCCOC3=CC=2)C=2C(=CC=C3OCCOC3=2)P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)=C1 ODEFOLDKAQTMMX-UHFFFAOYSA-N 0.000 description 1
- VBJSMXMZJPYREA-UHFFFAOYSA-N [7-(6-diphenylphosphanyl-2,3-dihydro-1-benzofuran-7-yl)-2,3-dihydro-1-benzofuran-6-yl]-diphenylphosphane Chemical compound C=12OCCC2=CC=C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1C1=C2OCCC2=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VBJSMXMZJPYREA-UHFFFAOYSA-N 0.000 description 1
- NVDNAKSQNFTFDM-UHFFFAOYSA-N [8-[7-bis(3,5-dimethylphenyl)phosphanyl-4-methyl-2,3-dihydro-1,4-benzoxazin-8-yl]-4-methyl-2,3-dihydro-1,4-benzoxazin-7-yl]-bis(3,5-dimethylphenyl)phosphane Chemical compound CN1CCOC(C=2C=3C(=CC=C4N(C)CCOC4=3)P(C=3C=C(C)C=C(C)C=3)C=3C=C(C)C=C(C)C=3)=C1C=CC=2P(C=1C=C(C)C=C(C)C=1)C1=CC(C)=CC(C)=C1 NVDNAKSQNFTFDM-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- YGXMUPKIEHNBNQ-UHFFFAOYSA-J benzene;ruthenium(2+);tetrachloride Chemical compound Cl[Ru]Cl.Cl[Ru]Cl.C1=CC=CC=C1.C1=CC=CC=C1 YGXMUPKIEHNBNQ-UHFFFAOYSA-J 0.000 description 1
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 1
- QREJTAJOJHAEQT-UHFFFAOYSA-N bis(3,5-dimethylphenyl)-pentylphosphane Chemical compound C1(=CC(=CC(=C1)C)C)P(C1=CC(=CC(=C1)C)C)CCCCC QREJTAJOJHAEQT-UHFFFAOYSA-N 0.000 description 1
- PPYKRIVFPTWIJA-UHFFFAOYSA-N bis(3,5-dimethylphenyl)phosphanylmethyl-bis(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(P(CP(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)=C1 PPYKRIVFPTWIJA-UHFFFAOYSA-N 0.000 description 1
- KTQVZDWGCQDVSP-UHFFFAOYSA-N bis(3,5-dimethylphenyl)phosphanyloxy-bis(3,5-dimethylphenyl)phosphane Chemical compound O(P(C1=CC(=CC(=C1)C)C)C1=CC(=CC(=C1)C)C)P(C1=CC(=CC(=C1)C)C)C1=CC(=CC(=C1)C)C KTQVZDWGCQDVSP-UHFFFAOYSA-N 0.000 description 1
- ICFJFBGAFIUVKS-UHFFFAOYSA-N bis(3,5-ditert-butylphenyl)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(PC=2C=C(C=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ICFJFBGAFIUVKS-UHFFFAOYSA-N 0.000 description 1
- FWKICRREDMVWRF-UHFFFAOYSA-N bis(4-methoxyphenyl)phosphane Chemical compound C1=CC(OC)=CC=C1PC1=CC=C(OC)C=C1 FWKICRREDMVWRF-UHFFFAOYSA-N 0.000 description 1
- RZWMJWOSBDZJOP-UHFFFAOYSA-N bis(4-methylphenyl)-(3-pyridin-3-ylpyridin-2-yl)phosphane Chemical compound CC1=CC=C(C=C1)P(C1=CC=C(C=C1)C)C1=NC=CC=C1C=1C=NC=CC=1 RZWMJWOSBDZJOP-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- FWXAUDSWDBGCMN-ZEQRLZLVSA-N chiraphos Chemical compound C=1C=CC=CC=1P([C@@H](C)[C@H](C)P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 FWXAUDSWDBGCMN-ZEQRLZLVSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- NZNMSOFKMUBTKW-UHFFFAOYSA-M cyclohexanecarboxylate Chemical compound [O-]C(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-M 0.000 description 1
- BDHBEHNAJFFXSS-UHFFFAOYSA-N cyclohexyl-[2-(4-methoxyphenyl)ethyl]phosphane Chemical compound C1=CC(OC)=CC=C1CCPC1CCCCC1 BDHBEHNAJFFXSS-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- VJVGVDCTJLFWMY-UHFFFAOYSA-N dicyclohexyl-[1-(2-dicyclohexylphosphanylnaphthalen-1-yl)naphthalen-2-yl]phosphane Chemical group C1CCCCC1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C1CCCCC1)C1CCCCC1)C1CCCCC1 VJVGVDCTJLFWMY-UHFFFAOYSA-N 0.000 description 1
- HDULBKVLSJEMGN-UHFFFAOYSA-N dicyclohexylphosphane Chemical compound C1CCCCC1PC1CCCCC1 HDULBKVLSJEMGN-UHFFFAOYSA-N 0.000 description 1
- WLLHDCZHPMDDPJ-UHFFFAOYSA-N dicyclopentyl-[1-(2-dicyclopentylphosphanyl-5,6,7,8-tetrahydronaphthalen-1-yl)-5,6,7,8-tetrahydronaphthalen-2-yl]phosphane Chemical group C1CCCC1P(C=1C(=C2CCCCC2=CC=1)C=1C(=CC=C2CCCCC2=1)P(C1CCCC1)C1CCCC1)C1CCCC1 WLLHDCZHPMDDPJ-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- SIIHBLVVANIZHU-UHFFFAOYSA-N diphenyl-(3-pyridin-3-ylpyridin-2-yl)phosphane Chemical compound C1=CC=CC=C1P(C=1C(=CC=CN=1)C=1C=NC=CC=1)C1=CC=CC=C1 SIIHBLVVANIZHU-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- VJYFKVYYMZPMAB-UHFFFAOYSA-N ethoprophos Chemical compound CCCSP(=O)(OCC)SCCC VJYFKVYYMZPMAB-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 150000002244 furazanes Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000006343 heptafluoro propyl group Chemical group 0.000 description 1
- 125000005549 heteroarylene group Chemical group 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- CBXWICRJSHEQJT-UHFFFAOYSA-N n,1-diphenylethanimine Chemical compound C=1C=CC=CC=1C(C)=NC1=CC=CC=C1 CBXWICRJSHEQJT-UHFFFAOYSA-N 0.000 description 1
- XPNLGBYLRMNJEP-UHFFFAOYSA-N n,2-diphenylethanimine Chemical compound C=1C=CC=CC=1CC=NC1=CC=CC=C1 XPNLGBYLRMNJEP-UHFFFAOYSA-N 0.000 description 1
- JATCPLSBWDXCNE-UHFFFAOYSA-N n-benzyl-1-phenylethanimine Chemical compound C=1C=CC=CC=1C(C)=NCC1=CC=CC=C1 JATCPLSBWDXCNE-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- VYMDGNCVAMGZFE-UHFFFAOYSA-N phenylbutazonum Chemical compound O=C1C(CCCC)C(=O)N(C=2C=CC=CC=2)N1C1=CC=CC=C1 VYMDGNCVAMGZFE-UHFFFAOYSA-N 0.000 description 1
- RVZJVYCTFGOEHX-UHFFFAOYSA-N phosphetane Chemical group C1CPC1 RVZJVYCTFGOEHX-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- ZBJSHDVMDCJOEZ-UHFFFAOYSA-N potassium;1h-naphthalen-1-ide Chemical compound [K+].[C-]1=CC=CC2=CC=CC=C21 ZBJSHDVMDCJOEZ-UHFFFAOYSA-N 0.000 description 1
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- JDNQPKBFOBQRBN-UHFFFAOYSA-N ruthenium monohydride Chemical compound [RuH] JDNQPKBFOBQRBN-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- BFMKBYZEJOQYIM-UHFFFAOYSA-N tert-butyl 4-diphenylphosphanyl-2-(diphenylphosphanylmethyl)pyrrolidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)CC1CP(C=1C=CC=CC=1)C1=CC=CC=C1 BFMKBYZEJOQYIM-UHFFFAOYSA-N 0.000 description 1
- DRZBLHZZDMCPGX-UHFFFAOYSA-N tert-butyl-[3-[tert-butyl(methyl)phosphanyl]quinoxalin-2-yl]-methylphosphane Chemical compound C1=CC=C2N=C(P(C)C(C)(C)C)C(P(C)C(C)(C)C)=NC2=C1 DRZBLHZZDMCPGX-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/16—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B53/00—Asymmetric syntheses
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/42—Benzopyrazines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
- C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
- C07D265/36—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings condensed with one six-membered ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
それらの問題点を解決するために、近年プロキラルな炭素−窒素二重結合の触媒的不斉水素化反応による合成法が盛んに研究されてきた。最近の総説にはロジウム、イリジウム、ルテニウム、パラジウム、チタンを中心金属とする錯体を用いる方法が述べられている(非特許文献1〜3参照)。これらの総説には高価なロジウム金属やイリジウム金属を用いた例は非常に多く、高収率で高立体選択的に光学活性アミン化合物が得られることが報告されている。しかしながら、比較的安価なルテニウム金属を用いた場合、生成するアミン化合物によりルテニウム錯体の活性が失われる場合があるため、広い基質適用性を有する炭素−酸素二重結合の不斉水素化反応に比べて、その利用は限られていると記載されている(非特許文献2)。
ルテニウム錯体と水素ガスを用いた炭素−窒素二重結合の触媒的不斉水素化反応の例として以下の文献が挙げられる。RuCl2(diphosphine)(diamine)と塩基を用いて種々のプロキラルなイミンの不斉水素化反応では、非環式のイミンであるN−(フェニルエチリデン)アニリンは最高92%eeで不斉水素化されたが、環式のイミンである2−メチルキノキサリンでは69%ee に低下する(特許文献1又は非特許文献4)。RuCl2[(S)−Hexahemp][(S,S)−DACH]を用いた2−メチルキノキサリンの不斉水素化反応では最高81%eeと、中程度の光学純度のアミンしか得られていない(特許文献2)。Ru(p−cymene)(monosulfonylated diamine)(BArF)を用いた2-メチルキノキサリンの不斉水素化では、1mol%の触媒量では98%eeの高い光学純度のアミンが得られているが、触媒量を0.1mol%まで減らすと93%eeまで低下する(非特許文献5)。
また、3-置換−2H−1,4−ベンゾキサジンの不斉水素化反応は、Ir−ジホスフィン錯体を用いた例があるが、価格が比較的安価なRu金属を用いた例は報告されていない(非特許文献6)。
即ち、本発明は、ルテナビシクロ構造を有するルテニウム錯体を用いた不斉還元による光学活性アミンの製造方法を提供する。
本発明は以下の[1]〜[6]の内容を含むものである。
[1]下記一般式(1)又は(2)
で表されるルテニウム錯体の存在下、プロキラルな炭素−窒素二重結合を不斉水素化することを特徴とする光学活性アミン類の製造方法。
[2]ルテニウム錯体が、下記一般式(3)又は(4)
で表される前記[1]に記載の製造方法。
[3]P⌒Pで表される光学活性ジホスフィンが、下記一般式(5)
R1R2P−Q−PR3R4 (5)
(式中、R1、R2、R3及びR4は、それぞれ独立して置換基を有していてもよいアリール基、置換基を有していてもよいシクロアルキル基、又は置換基を有していてもよいアルキル基を表し、R1とR2とで及び/又はR3とR4とで環を形成してもよい。Qは不斉構造を有し、置換基を有していてもよい、ビフェニルジイル基、ビナフタレンジイル基、ビピリジンジイル基、パラシクロファンジイル基、又はフェロセンジイル基を表す。)
で表されるジホスフィンである前記[1]又は[2]のいずれかに記載の製造方法。
[4]P⌒Pが、下記一般式(6)で表される光学活性ジホスフィンである前記[3]に記載の製造方法。
[5]一般式(5)におけるR1、R2、R3及びR4、並びに一般式(6)におけるR1'、R2'、R3'及びR4'が、3,5−キシリル基である前記[3]又は[4]のいずれかに記載の製造方法。
[6]塩基化合物の存在下で行われる、前記[1]〜[5]のいずれかに記載の製造方法。
直鎖又は分岐のアルキル基としては、例えば炭素数1〜10、好ましくは炭素数1〜6、より好ましくは炭素数1〜4の直鎖又は分岐のアルキル基が挙げられ、該アルキル基はフッ素原子等のハロゲン原子で置換されていてもよく、具体的にはメチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、イソブチル基、s−ブチル基、t−ブチル基、トリフルオロメチル基等が挙げられる。
直鎖又は分岐のアルコキシ基としては、例えば炭素数1〜10、好ましくは炭素数1〜6、より好ましくは炭素数1〜4の直鎖又は分岐のアルコキシ基が挙げられ、具体的にはメトキシ基、エトキシ基、n−プロポキシ基、イソプロポキシ基、n−ブトキシ基、s−ブトキシ基、イソブトキシ基及びt−ブトキシ基などが挙げられる。
シクロアルキル基としては、炭素数3〜15、好ましくは炭素数5〜7の飽和又は不飽和の単環式、多環式又は縮合環式のシクロアルキル基が挙げられ、具体的にはシクロペンチル基、シクロヘキシル基などが挙げられる。これらシクロアルキル基の環上においては、炭素数1〜4のアルキル基又は炭素数1〜4のアルコキシ基で、1又は2以上置換されていてもよい。
ハロゲン原子としては、塩素原子、臭素原子、ヨウ素原子、フッ素原子等が挙げられる。
ヘテロアリール基としては、酸素原子、硫黄原子、窒素原子等を含む5員環又は6員環状の基が挙げられ、具体的にはフリル基、チエニル基、ピリジル基等が挙げられる。
三置換シリル基としては、前記したアルキル基やアリール基で三置換されたシリル基が挙げられ、例えばトリメチルシリル基、トリエチルシリル基、トリイソプロピルシリル基、tert−ブチルジメチルシリル基、ジフェニルメチルシリル基、ジメチルフェニルシリル基などが挙げられる。
C1〜C20アルキル基としては、炭素数1〜20、好ましくは炭素数1〜5、より好ましくは炭素数1〜4の直鎖状又は分枝状のアルキル基が挙げられ例えば、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、イソブチル基、sec−ブチル基、t−ブチル基、n−ペンチル基、n−ヘキシル基、デシル基、ドデシル基、ヘキサデシル基等が挙げられる。
C2〜C20アルケニル基としては、炭素数2〜20、好ましくは炭素数2〜10、より好ましくは炭素数2〜6の直鎖状又は分枝状のアルケニル基が挙げられ、例えば、エテニル基、n−プロペニル基、イソプロペニル基、1−ブテニル基、1−ブテン−2−イル基、ペンテニル基、ヘキセニル基等が挙げられる。
C1〜C20アルコキシ基としては、前記した炭素数1〜20のアルキル基に酸素原子結合した基が挙げられる。例えば、メトキシ基、エトキシ基、n−プロポキシ基、イソプロポキシ基、n−ブトキシ基、s−ブトキシ基、イソブトキシ基及びt−ブトキシ基などが挙げられる。
炭素数1〜5のハロゲン化アルキル基としては、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、トリクロロメチル基などが挙げられる。
ハロゲン原子としては、塩素原子、臭素原子、フッ素原子等が挙げられる。
ヘテロアリール基としては、酸素原子、硫黄原子、窒素原子等を含む5員環又は6員環状の基が挙げられ、具体的にはフリル基、チエニル基、ピリジル基等が挙げられる。
三置換シリル基としては、前記したアルキル基やアリール基で三置換されたシリル基が挙げられ、例えばトリメチルシリル基、トリエチルシリル基、トリイソプロピルシリル基、tert−ブチルジメチルシリル基、ジフェニルメチルシリル基、ジメチルフェニルシリル基などが挙げられる。
C7〜C20アラルキル基としては、炭素数6〜20、好ましくは炭素数6〜14の単環式、多環式、又は縮合環式のアリール基に、前記した炭素数1〜19のアルキル基が結合した、炭素数7〜20、好ましくは炭素数7〜15、炭素数7〜10のアラルキル基が挙げられる。例えば、ベンジル基、α−メチルベンジル基、α,α−ジメチルベンジル基、2−フェニルエチル基、3−フェニルプロピル基等が挙げられる。
置換基を有していてもよいアリール基のアリール基としては、炭素数6〜20、好ましくは炭素数6〜14、炭素数6〜12の単環式、多環式、又は縮合環式のアリール基が挙げられる。具体的にはフェニル基、ナフチル基、アントリル基、フェナントリル基、ビフェニル基などが挙げられ、フェニル基が好ましい。これらアリール基は1又は2以上の置換基を有していてもよく、該置換基としては、前述したようなメチル基、イソプロピル基及びt−ブチル基等の炭素数1〜4のアルキル基;メトキシ基、エトキシ基、n−プロポキシ基、イソプロポキシ基、n−ブトキシ基、イソブトキシ基、s−ブトキシ基及びt−ブトキシ基等の炭素数1〜4のアルコキシ基などが挙げられる。
RbとRcとで形成するアルキレンジオキシ基としては、炭素数1〜6、好ましくは炭素数1〜4の直鎖又は分岐のアルキレンジオキシ基が挙げられる。例えば、メチレンジオキシ基、エチレンジオキシ基、トリメチレンジオキシ基等が挙げられる。
RN1とRaとで形成するアルキレン基としては、炭素数1〜6、好ましくは炭素数1〜4の直鎖又は分岐のアルキレン基が挙げられる。例えば、メチレン基、エチレン基、トリメチレン基、プロピレン基、テトラメチレン基等が挙げられ、これらアルキレン基は炭素数1〜4のアルキル基、炭素数1〜4のアルコキシ基で置換されていてもよい。
上記式中、R1、R2、R3及びR4で表される、置換基を有していてもよいアリール基としては、例えば炭素数6〜14のアリール基が挙げられ、具体的にはフェニル基、ナフチル基、アントリル基、フェナントリル基、ビフェニル基などが挙げられる。
これらアリール基は1又は2以上の置換基を有していてもよく、該置換基としては、アルキル基、アルコキシ基などが挙げられる。
前記アリール基の置換基としてのアルコキシ基としては、直鎖状又は分岐状の、例えば炭素数1〜6のアルコキシ基が挙げられ、具体的にはメトキシ基、エトキシ基、n−プロポキシ基、イソプロポキシ基、n−ブトキシ基、s−ブトキシ基、イソブトキシ基及びt−ブトキシ基などが挙げられる。
置換基を有していてもよいアルキル基としては、直鎖状又は分岐状の、例えば炭素数1〜15、好ましくは炭素数1〜10、より好ましくは炭素数1〜6のアルキル基が挙げられ、具体例としては、例えばメチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、s−ブチル基、イソブチル基及びt−ブチル基などが挙げられる。これらのアルキル基においては、前記アリール基の置換基として挙げたようなアルコキシ基などの置換基で、1又は2以上置換されていてもよい。
ビフェニルジイル基、ビナフタレンジイル基及びビピリジンジイル基としては、軸不斉構造を有する1,1'−ビアリール−2,2'−ジイル型の構造を有するものが好ましく、該ビフェニルジイル基、ビナフタレンジイル基及びビピリジンジイル基は、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、s−ブチル基、イソブチル基及びt−ブチル基などの炭素数1〜6のアルキル基;メトキシ基、エトキシ基、n−プロポキシ基、イソプロポキシ基、n−ブトキシ基、s−ブトキシ基、イソブトキシ基及びt−ブトキシ基などの炭素数1〜6のアルコキシ基;メチレンジオキシ基、エチレンジオキシ基、トリメチレンジオキシ基などのアルキレンジオキシ基;水酸基;アミノ基;又は置換アミノ基などで置換されていてもよい。
また、フェロセンジイル基も置換基を有していてもよく、置換基としては、前記したようなアルキル基、アルコキシ基、アルキレンジオキシ基、水酸基、アミノ基、置換アミノ基などが挙げられる。
これらの置換アミノ基としては、1個又は2個の炭素数1〜6のアルキルで置換されたアミノ基が挙げられる。
R)−6,7−ジメチル−6,7−ジヒドロジベンゾ[e,g][1,4]ジオキソシン−1,12−ジイル)ビス(ジ(3,5−キシリル)ホスフィン)、(4,4',5,5',6,6'−ヘキサメチルビフェニル−2,2'−ジイル)ビス(ジフェニルホスフィン)、(4,4',5,5',6,6'−ヘキサメチルビフェニル−2,2'−ジイル)ビス(ジ(3,5−キシリル)ホスフィン)、(4,4',5,5',6,6'−ヘキサメトキシビフェニル−2,2'−ジイル)ビス(ジフェニルホスフィン)、(4,4',5,5',6,6'−ヘキサメトキシビフェニル−2,2'−ジイル)ビス(ジ(3,5−キシリル)ホスフィン)、(5,5'−ジクロロ−4,4',6,6'−テトラメチルビフェニル−2,2'−ジイル)ビス(ジフェニルホスフィン)、(5,5'−ジクロロ−4,4',6,6'−テトラメチルビフェニル−2,2'−ジイル)ビス(ジ(3,5−キシリル)ホスフィン)、(5,5'−ジメトキシ−4,4',6,6'−テトラメチルビフェニル−2,2'−ジイル)ビス(ジフェニルホスフィン)、(5,5'−ジメトキシ−4,4',6,6'−テトラメチルビフェニル−2,2'−ジイル)ビス(ジ(3,5−キシリル)ホスフィン)、2,2'−ビス(ジフェニルホスフィノ)−6,6'−ジメトキシビフェニル−3,3'−ジオール、2,2'−ビス(ジ(3,5−キシリル)ホスフィノ)−6,6'−ジメトキシビフェニル−3,3'−ジオール、(3,3',6,6'−テトラメトキシビフェニル−2,2'−ジイル)ビス(ジフェニルホスフィン)、(3,3',6,6'−テトラメトキシビフェニル−2,2'−ジイル)ビス(ジ(3,5−キシリル)ホスフィン)、(3,3'−ジイソプロピル−6,6'−ジメトキシビフェニル−2,2'−ジイル)ビス(ジフェニルホスフィン)、(3,3'−ジイソプロピル−6,6'−ジメトキシビフェニル−2,2'−ジイル)ビス(ジ(3,5−キシリル)ホスフィン)、(6,6'−ジメトキシ−3,3'−ビス(p−トリルオキシ)ビフェニル−2,2'−ジイル)ビス(ジフェニルホスフィン)、(6,6'−ジメトキシ−3,3'−ビス(p−トリルオキシ)ビフェニル−2,2'−ジイル)ビス(ジ(3,5−キシリル)ホスフィン)、2,2'−ビス(ジフェニルホスフィノ)−6,6'−ジメトキシビフェニル−3,3'−ジイルビス(2,2−ジメチルプロパノエート)、2,2'−ビス(ジ(3,5−キシリル)ホスフィノ)−6,6'−ジメトキシビフェニル−3,3'−ジイルビス(2,2−ジメチルプロパノエート)、(5,5'−ジクロロ−6,6'−ジメトキシビフェニル−2,2'−ジイル)ビス(ジフェニルホスフィン)、(5,5'−ジクロロ−6,6'−ジメトキシビフェニル−2,2'−ジイル)ビス(ジ(3,5−キシリル)ホスフィン)、6,6'−ビス(ジフェニルホスフィノ)ビフェニル−2,2'−ジイル ジアセテート、6,6'−ビス(ジ(3,5−キシリル)ホスフィノ)ビフェニル−2,2'−ジイル ジアセテート、6,6'−ビス(ジフェニルホスフィノ)ビフェニル−2,2'−ジイルビス(2,2−ジメチルプロパノエート)、6,6'−ビス(ジ(3,5−キシリル)ホスフィノ)ビフェニル−2,2'−ジイルビス(2,2−ジメチルプロパノエート)、6,6'−ビス(ジフェニルホスフィノ)ビフェニル−2,2'−ジイルビス(2−メチルプロパノエート)、6,6'−ビス(ジ(3,5−キシリル)ホスフィノ)ビフェニル−2,2'−ジイルビス(2−メチルプロパノエート、6,6'−ビス(ジフェニルホスフィノ)ビフェニル−2,2'−ジイル ジシクロヘキサンカルボキシレート、6,6'−ビス(ジ(3,5−キシリル)ホスフィノ)ビフェニル−2,2'−ジイル ジシクロヘキサンカルボキシレート、(4,4',6,6'−テトラキス(トリフルオロメチル)ビフェニル−2,2'−ジイル)ビス(ジフェニルホスフィン)、(4,4',6,6'−テトラキス(トリフルオロメチル)ビフェニル−2,2'−ジイル)ビス(ジ(3,5−キシリル)ホスフィン)、(5−メトキシ−4,6−ジメチル−4',6'−ビス(トリフルオロメチル)ビフェニル−2,2'−ジイル)ビス(ジフェニルホスフィン)、(5−メトキシ−4,6−ジメチル−4',6'−ビス(トリフルオロメチル)ビフェニル−2,2'−ジイル)ビス(ジ(3,5−キシリル)ホスフィン)、(2,2,2',2'−テトラメチル−4,4'−ビベンゾ[d][1,3]ジオキソール−5,5'−ジイル)ビス(ジフェニルホスフィン)、(2,2,2',2'−テトラメチル−4,4'−ビベンゾ[d][1,3]ジオキソール−5,5'−ジイル)ビス(ジ(3,5−キシリル)ホスフィン)、6,6'−ビス(ジフェニルホスフィノ)−2,2',3,3'−テトラヒドロ−7,7'−ビベンゾフラン、6,6'−ビス(ジ(3,5−キシリル)ホスフィノ)−2,2',3,3'−テトラヒドロ−7,7'−ビベンゾフラン、(2,2,2',2'−テトラフルオロ−4,4'−ビベンゾ[d][1,3]ジオキソール−5,5'−ジイル)ビス(ジフェニルホスフィン)、(2,2,2',2'−テトラフルオロ−4,4'−ビベンゾ[d][1,3]ジオキソール−5,5'−ジイル)ビス(ジ(3,5−キシリル)ホスフィン)、2−(ナフチル)−8−ジフェニルホスフィノ−1−[3,5−ジオサ−4−ホスファ−シクロヘプタ[2,1−a;3,4−a']ジナフタレン−4−イル]−1,2−ジヒドロキノリン、4,12−ビス(ジ(3,5−キシリル)ホスフィノ)−[2.2]−パラシクロファン、7,7'−ビス(ジ(3,5−キシリル)ホスフィノ)−2,2',3,3'−テトラヒドロ−1,1'−スピロビインダン(Xyl-SDP)、7,7'−ビス(ジフェニルホスフィノ)−2,2',3,3'−テトラヒドロ−1,1'−スピロビインダン(SDP)、ビス(2−ジフェニルホスフィノフェニル)エーテル(DPEphos)、4,5−ビス(ジフェニルホスフィノメチル)−2,2−ジメチル−1,3−ジオキソラン(DIOP)、1,2−ビス(ジフェニルホスフィノ)プロパン(PROPHOS)、2,3−ビス(ジフェニルホスフィノ)ブタン(CHIRAPHOS)、1,2−ビス[(2−メトキシフェニル)(フェニル)ホスフィノ]エタン(DIPAMP)、3,4−ビス(ジフェニルホスフィノ)−1−ベンジルピロリジン(DEGUPHOS)、2,3−ビス(ジフェニルホスフィノ)−ビシクロ[2.2.1]ヘプト−5−エン(NORPHOS)、1−ターシャリーブトキシカルボニル−4−ジフェニルホスフィノ−2−(ジフェニルホスフィノメチル)ピロリジン(BPPM)、(2,2'−ビス−(ジベンゾフラン−3,3−ジイル)−ビス−ジフェニルホスフィン(BIBFUP)、2,2‐ビス(ジフェニルホスフィノ)‐3,3‐ビナフト[b]フラン(BINAPFu)、2,2'‐ビス(ジフェニルホスフィノ)‐3,3'‐ビ[ベンゾ[b]チオフェン](BITIANP)、N,N'−ジメチル−7,7'−ビス(ジ(3,5−キシリル)ホスフィノ)−3,3',4,4'−テトラヒドロ−8,8'−ビ−2H−1,4−ベンズオキサジン(Xyl-Solphos)2,3−ビス(ターシャリーブチルメチルホスフィノ)キノキサリン(QuinoxP*)、2,4−ビス(ジフェニルホスフィノ)ペンタン(SKEWPHOS)、2,4−ビス(ジ(3,5−キシリル)ホスフィノ)ペンタン(XylSKEWPHOS)、4,4'−ビス(ジフェニルホスフィノ)−2,2',5,5'−テトラメチル−3,3'−ビチオフェン(TMBTP)、3,3'−ビス(ジフェニルホスホニル)−1,1'−2,2'−ビインドール(N-Me-2-BINPO)、(2,2',5,5'−テトラメチル−3,3'−ビチオフェン−4,4'−ジイル)ビス(ジフェニルホスフィン)(BITIANP)、(4,4',6,6'−テトラメチル−3,3'−ビベンゾ[b]チオフェン−2,2'−ジイル)ビス(ジフェニルホスフィン)(tetraMe-BITIANP)、1,1'−ビス(ジフェニルホスフィノ)−3,3'−ジメチル−1H,1'H−2,2'−ビインドール(BISCAP)、2,2'−ビス(ジフェニルホスフィノ)−3,3'−ビベンゾフラン(BICUMP)、2,2'−ビス(ジフェニルホスフィノ)−1,1'−ビベンゾ[d]イミダゾール(BIMIP)などが挙げられる。
[RuX'(L)(P⌒P)]X' (A)
(式(A)中、Ruはルテニウム原子を示し、X'はアニオン性基を示し、Lはアレーンを示し、P⌒Pは光学活性ジホスフィンを示す。)
[Ru(X')2(L)]m (B)
(式(B)中、Ruはルテニウム原子を示し、X'はアニオン性基を示し、Lはアレーンを示し、mは2以上の自然数を示す。)
一般式(B)で示されるルテニウム化合物(以下、アレーン錯体ともいう。)は、市販されているもの、又は既報の方法に準じて製造することができる。また、一般式(A)で示されるルテニウム化合物(以下、アレーン−ホスフィン錯体ともいう。)は、市販されているもの、又は既報の方法に準じてP⌒Pで表される光学活性ジホスフィン化合物と、一般式(B)で示されるアレーン錯体とを反応させて製造することもできる。
以下、不斉水素化に関して説明する。
本発明のプロキラルな炭素−窒素二重結合の不斉水素化反応としては、式(12)
上記化合物(C)及び(D)のR21、R22及びR23のアルキル基としては、例えば炭素数1〜8の炭素数のアルキル基が挙げられ、(ヘテロ)アリール基としては、フェニル、ナフチル、ピリジル、ピリミジニル、フリル、チエニルなどが挙げられ、置換基としては、炭素数1〜6のアルキル基、炭素数1〜6のアルコキシ基、ハロゲン原子等が挙げられる。アラルキル基のアルキルとしては炭素数1〜12のものが挙げられる。この種の代表的なイミン基質は、N−(1−フェニルエチリデン)アニリンやN−(1−フェニルエチリデン)ベンジルアミン等が挙げられる。
実施例によって限定されるものではない。
実施例1において使用した触媒、基質と触媒のモル比、水素圧、反応温度、反応時間を表1に示すように変更した以外は、原料として2−メチルキノキサリンを用いて実施例1と同様の方法で反応を実施した。1,2,3,4−テトラヒドロ−2−メチルキノキサリンの収率は、実施例1と同様に、反応後、水素を開放した後、溶液を減圧下濃縮し、残渣を1H NMRにて測定した。光学純度も実施例1と同様に、ガスクロマトグラフィー(カラム:CHIRASIL−DEX CB)を用いて測定した。反応結果を表1に示す。
実施例1〜9及び比較例1との比較から、比較例1の触媒活性は実施例1〜9の触媒活性の2分の1以下にとどまり、得られる生成物の光学純度も低いことを確認した。
Claims (3)
- 下記一般式(3)又は(4)
(式中、P⌒Pは、下記一般式(6)で表される光学活性ジホスフィンを表し、
Xはアニオン性基を表す。R a 、R b 及びR c はそれぞれ独立して水素原子、置換基を有してもよいC 1 〜C 20 アルキル基、置換基を有してもよいC 2 〜C 20 アルケニル基、置換基を有してもよいC 3 〜C 8 シクロアルキル基、置換基を有してもよいC 7 〜C 20 アラルキル基、置換基を有してもよいアリール基、又は置換基を有してもよいヘテロ環基を表すか、R b とR c とで置換基を有してもよいアルキレン基又は置換基を有してもよいアルキレンジオキシ基を形成してもよい。R d 、R e 、R f 、R g はそれぞれ独立して水素原子、置換基を有してもよいC 1 〜C 20 アルキル基、C 1 〜C 5 ハロゲン化アルキル基、ハロゲン原子、置換基を有してもよいアリール基、置換基を有してもよいC 3 〜C 8 シクロアルキル基、三置換シリル基又は置換基を有してもよいC 1 〜C 20 アルコキシ基を表す。R N1 、R N2 、R N3 及びR N4 はそれぞれ独立して水素原子、置換基を有してもよいC 1 〜C 20 アルキル基、置換基を有してもよいC 2 〜C 20 アルケニル基、置換基を有してもよいC 7 〜C 20 アラルキル基、又は置換基を有してもよいC 3 〜C 8 シクロアルキル基を表し、R N1 、R N2 、R N3 及びR N4 のうち少なくとも一つは水素原子である。また、R N1 とR a とで置換基を有してもよいアルキレン基を形成してもよい。)で表されるルテニウム錯体の存在下、プロキラルな炭素−窒素二重結合を不斉水素化する光学活性アミン化合物の製造方法であって、
プロキラルな炭素−窒素二重結合を不斉水素化が、下記式(13)
下記式(14)
- 一般式(6)におけるR1'、R2'、R3'及びR4'が、3,5−キシリル基である請求項1に記載の製造方法。
- 塩基化合物の存在下で行われる、請求項1又は2に記載の製造方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012197246A JP6065259B2 (ja) | 2012-09-07 | 2012-09-07 | 光学活性アミン類の製造方法 |
US14/421,481 US9328079B2 (en) | 2012-09-07 | 2013-09-06 | Process for producing optically active amine |
PCT/JP2013/074109 WO2014038666A1 (ja) | 2012-09-07 | 2013-09-06 | 光学活性アミン類の製造方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012197246A JP6065259B2 (ja) | 2012-09-07 | 2012-09-07 | 光学活性アミン類の製造方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2014051458A JP2014051458A (ja) | 2014-03-20 |
JP6065259B2 true JP6065259B2 (ja) | 2017-01-25 |
Family
ID=50237271
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2012197246A Active JP6065259B2 (ja) | 2012-09-07 | 2012-09-07 | 光学活性アミン類の製造方法 |
Country Status (3)
Country | Link |
---|---|
US (1) | US9328079B2 (ja) |
JP (1) | JP6065259B2 (ja) |
WO (1) | WO2014038666A1 (ja) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2695887A4 (en) * | 2011-04-06 | 2014-09-03 | Takasago Perfumery Co Ltd | NEW RUTHENIUM COMPLEX AND PROCESS FOR PRODUCTION OF OPTICALLY ACTIVE ALCOHOL COMPOUND USING AS CATALYST |
US10550139B2 (en) | 2014-06-09 | 2020-02-04 | Triad National Security, Llc | Polydentate ligands and their complexes for molecular catalysis |
US10487100B1 (en) | 2017-04-04 | 2019-11-26 | Triad National Security, Llc | Macrocyclic ligands and their complexes for bifunctional molecular catalysis |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9706321D0 (en) | 1997-03-26 | 1997-05-14 | Zeneca Ltd | Catalytic hydrogenation |
EP1299401B1 (en) | 2000-06-02 | 2004-03-31 | Chirotech Technology Limited | Chiral ligands for asymmetric catalysis |
JP2004504371A (ja) | 2000-07-24 | 2004-02-12 | カイロテック・テクノロジー・リミテッド | ルテニウム錯体および不斉水素化におけるその使用 |
WO2011135753A1 (en) * | 2010-04-28 | 2011-11-03 | Takasago International Corporation | Ruthenium complex and method for preparing optically active alcohol compound |
EP2695887A4 (en) | 2011-04-06 | 2014-09-03 | Takasago Perfumery Co Ltd | NEW RUTHENIUM COMPLEX AND PROCESS FOR PRODUCTION OF OPTICALLY ACTIVE ALCOHOL COMPOUND USING AS CATALYST |
-
2012
- 2012-09-07 JP JP2012197246A patent/JP6065259B2/ja active Active
-
2013
- 2013-09-06 US US14/421,481 patent/US9328079B2/en active Active
- 2013-09-06 WO PCT/JP2013/074109 patent/WO2014038666A1/ja active Application Filing
Also Published As
Publication number | Publication date |
---|---|
JP2014051458A (ja) | 2014-03-20 |
WO2014038666A1 (ja) | 2014-03-13 |
US20150210657A1 (en) | 2015-07-30 |
US9328079B2 (en) | 2016-05-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5685071B2 (ja) | 新規ルテニウム錯体及びこれを触媒とする光学活性アルコール化合物の製造方法 | |
US9255049B2 (en) | Ruthenium complex and method for preparing optically active alcohol compounds using the same as a catalyst | |
JP6065259B2 (ja) | 光学活性アミン類の製造方法 | |
JP5276093B2 (ja) | 光学活性アミノアルコール化合物の製造方法 | |
JP6254811B2 (ja) | 含窒素複素環カルベン配位子を有する有機金属化合物、これを含む触媒およびアミン化合物の製造方法 | |
JP3720235B2 (ja) | 光学活性ルテニウムホスフィン錯体の製造方法及び該錯体を用いた光学活性アルコールの製造方法 | |
JP6476497B2 (ja) | 光学活性化合物の製造方法、及び新規な金属−ジアミン錯体 | |
JP4682141B2 (ja) | イリジウム錯体 | |
JP2013177374A (ja) | 光学活性アミン化合物の製造方法 | |
JP5685046B2 (ja) | 光学純度低下防止方法 | |
JP2009235067A (ja) | 軸不斉リン化合物とその製造方法 | |
JP2008201760A (ja) | 光学活性スピロ化合物及びその製造方法 | |
US9340519B2 (en) | Paracyclophane-based ligands, their preparation and use in catalysis | |
ES2443994T3 (es) | Ligandos quirales para el uso en síntesis asimétricas | |
JP4562736B2 (ja) | 光学活性アルコールの製造方法 | |
EP2774908B1 (en) | Method for preventing decrease in optical purity | |
JP5552716B2 (ja) | 光学活性β−ケトニトリル化合物およびその製造方法 | |
JP2012031119A (ja) | 軸不斉イソキノリン誘導体及びその製造方法並びに不斉合成方法 | |
TWI510472B (zh) | 立體選擇性製備吡唑羧醯胺之方法 | |
JP2013082638A (ja) | 光学活性アミノニトリル化合物およびその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150903 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160912 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20161109 |
|
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: 20161205 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20161208 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6065259 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |