TWI422430B - 用於置換反應作用觸媒之新穎釕複合物 - Google Patents
用於置換反應作用觸媒之新穎釕複合物 Download PDFInfo
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- TWI422430B TWI422430B TW096123308A TW96123308A TWI422430B TW I422430 B TWI422430 B TW I422430B TW 096123308 A TW096123308 A TW 096123308A TW 96123308 A TW96123308 A TW 96123308A TW I422430 B TWI422430 B TW I422430B
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- Prior art keywords
- alkyl
- mmol
- group
- rucl
- compound
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title abstract description 20
- 238000005649 metathesis reaction Methods 0.000 title abstract 3
- 150000003303 ruthenium Chemical class 0.000 title 1
- 238000006798 ring closing metathesis reaction Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 42
- -1 2,4,6-trimethylphenyl Chemical group 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000000460 chlorine Substances 0.000 claims description 20
- 238000006073 displacement reaction Methods 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 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 4
- 125000006272 (C3-C7) cycloalkyl group Chemical group 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000005686 cross metathesis reaction Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- 239000013078 crystal Substances 0.000 description 20
- 125000003118 aryl group Chemical group 0.000 description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- XYMRZTIWXWDRCG-UHFFFAOYSA-N 1-(4-methylphenyl)sulfonyl-2,3-dihydropyrrole Chemical compound C1=CC(C)=CC=C1S(=O)(=O)N1C=CCC1 XYMRZTIWXWDRCG-UHFFFAOYSA-N 0.000 description 14
- 239000000725 suspension Substances 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 8
- UNYMIBRUQCUASP-UHFFFAOYSA-N 1-(4-methylphenyl)sulfonyl-2,5-dihydropyrrole Chemical compound C1=CC(C)=CC=C1S(=O)(=O)N1CC=CC1 UNYMIBRUQCUASP-UHFFFAOYSA-N 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 241000256844 Apis mellifera Species 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 125000004104 aryloxy group Chemical group 0.000 description 6
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 6
- 125000001639 phenylmethylene group Chemical group [H]C(=*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 125000001072 heteroaryl group Chemical group 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000004916 (C1-C6) alkylcarbonyl group Chemical group 0.000 description 3
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 239000013058 crude material Substances 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 125000006700 (C1-C6) alkylthio group Chemical group 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
- NUGBPIKQLKJUJM-UHFFFAOYSA-N 4-chloro-8-ethenyl-2-(trifluoromethyl)quinoline Chemical compound C1=CC=C(C=C)C2=NC(C(F)(F)F)=CC(Cl)=C21 NUGBPIKQLKJUJM-UHFFFAOYSA-N 0.000 description 2
- NXTRFMJLEVMUBV-UHFFFAOYSA-N 4-chloro-8-ethenylquinoline Chemical compound C1=CC=C2C(Cl)=CC=NC2=C1C=C NXTRFMJLEVMUBV-UHFFFAOYSA-N 0.000 description 2
- OKXHMBXWZHCSMR-UHFFFAOYSA-N 4-methyl-n,n-bis(prop-2-enyl)benzenesulfonamide Chemical compound CC1=CC=C(S(=O)(=O)N(CC=C)CC=C)C=C1 OKXHMBXWZHCSMR-UHFFFAOYSA-N 0.000 description 2
- LEUPFCDQAMPSGV-UHFFFAOYSA-N 8-ethenyl-2-methylquinoline Chemical compound C1=CC=C(C=C)C2=NC(C)=CC=C21 LEUPFCDQAMPSGV-UHFFFAOYSA-N 0.000 description 2
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 2
- 238000006546 Horner-Wadsworth-Emmons reaction Methods 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 125000002837 carbocyclic group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000006880 cross-coupling reaction Methods 0.000 description 2
- GDWAYKGILJJNBB-UHFFFAOYSA-N diethyl 2-prop-2-enylpropanedioate Chemical compound CCOC(=O)C(CC=C)C(=O)OCC GDWAYKGILJJNBB-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- SFDJOSRHYKHMOK-UHFFFAOYSA-N nitramide Chemical compound N[N+]([O-])=O SFDJOSRHYKHMOK-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 125000004454 (C1-C6) alkoxycarbonyl group Chemical group 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JGMAWQSXXGIRHJ-OWOJBTEDSA-N 2-[(E)-3-cyanoprop-2-enyl]propanedioic acid Chemical compound OC(=O)C(C(O)=O)C\C=C\C#N JGMAWQSXXGIRHJ-OWOJBTEDSA-N 0.000 description 1
- APKFPKLTEJAOJI-UHFFFAOYSA-N 6-butyldec-5-en-5-ylstannane Chemical compound CCCCC([SnH3])=C(CCCC)CCCC APKFPKLTEJAOJI-UHFFFAOYSA-N 0.000 description 1
- 125000003341 7 membered heterocyclic group Chemical group 0.000 description 1
- GQPRZSFQSOEDNV-UHFFFAOYSA-N 8-bromo-2-methylquinoline Chemical compound C1=CC=C(Br)C2=NC(C)=CC=C21 GQPRZSFQSOEDNV-UHFFFAOYSA-N 0.000 description 1
- PWMOSSSZBKQCEA-UHFFFAOYSA-N 8-bromo-2-phenyl-1h-quinolin-4-one Chemical compound BrC1=CC=CC(C(C=2)=O)=C1NC=2C1=CC=CC=C1 PWMOSSSZBKQCEA-UHFFFAOYSA-N 0.000 description 1
- KKGSBQKOZKBRKL-UHFFFAOYSA-N 8-bromo-4-chloro-2-(trifluoromethyl)quinoline Chemical compound C1=CC=C(Br)C2=NC(C(F)(F)F)=CC(Cl)=C21 KKGSBQKOZKBRKL-UHFFFAOYSA-N 0.000 description 1
- DAHYJSFUKJLEEJ-UHFFFAOYSA-N 8-bromo-4-chloroquinoline Chemical compound C1=CC=C2C(Cl)=CC=NC2=C1Br DAHYJSFUKJLEEJ-UHFFFAOYSA-N 0.000 description 1
- FIQFOHUIGOAPDK-UHFFFAOYSA-N 8-ethenyl-2-(trifluoromethyl)quinoline Chemical compound FC(C1=NC2=C(C=CC=C2C=C1)C=C)(F)F FIQFOHUIGOAPDK-UHFFFAOYSA-N 0.000 description 1
- BXPIWOKCXUBWKM-UHFFFAOYSA-N 8-ethenyl-2-phenyl-1h-quinolin-4-one Chemical compound N=1C2=C(C=C)C=CC=C2C(O)=CC=1C1=CC=CC=C1 BXPIWOKCXUBWKM-UHFFFAOYSA-N 0.000 description 1
- WRTNGGDLQMFSJL-UHFFFAOYSA-N 8-ethenylquinoline Chemical compound C1=CN=C2C(C=C)=CC=CC2=C1 WRTNGGDLQMFSJL-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- JCVSJAVKWHMGTE-UHFFFAOYSA-N diethyl 2-(3-cyanoprop-2-enyl)propanedioate Chemical compound CCOC(=O)C(C(=O)OCC)CC=CC#N JCVSJAVKWHMGTE-UHFFFAOYSA-N 0.000 description 1
- JCVSJAVKWHMGTE-WAYWQWQTSA-N diethyl 2-[(z)-3-cyanoprop-2-enyl]propanedioate Chemical compound CCOC(=O)C(C(=O)OCC)C\C=C/C#N JCVSJAVKWHMGTE-WAYWQWQTSA-N 0.000 description 1
- HHRKFGMMAHZWIM-UHFFFAOYSA-N ethenoxyboronic acid Chemical compound OB(O)OC=C HHRKFGMMAHZWIM-UHFFFAOYSA-N 0.000 description 1
- RWMJRMPOKXSHHI-UHFFFAOYSA-N ethenylboron Chemical compound [B]C=C RWMJRMPOKXSHHI-UHFFFAOYSA-N 0.000 description 1
- BADWIIDKTXQYLW-UHFFFAOYSA-N ethenylstannane Chemical compound [SnH3]C=C BADWIIDKTXQYLW-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-M methanesulfonate group Chemical class CS(=O)(=O)[O-] AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([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
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical class CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000005951 trifluoromethanesulfonyloxy group Chemical group 0.000 description 1
- XBEADGFTLHRJRB-UHFFFAOYSA-N undecylbenzene Chemical compound CCCCCCCCCCCC1=CC=CC=C1 XBEADGFTLHRJRB-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Description
本發明係關於下式之新穎置換反應觸媒
其製造方法及其在置換反應例如閉環置換反應或交叉置換反應中的用途。
吾人已熟知使用釕或其他過渡金屬複合物作為觸媒之置換反應且同時已將其廣泛應用於有機合成中(參見(例如)WO 2004/035596、WO 2002/14376或歐洲專利第EP-A 1180108號)。
下式之置換反應觸媒
由Barbasiewicz等人在2006年6月17日萬維網上發表的Organometallics中進行了闡釋。作者指出,在室溫下將此觸媒應用於N,N-二烯丙基-4-甲基苯磺醯胺在二氯甲烷中的閉環置換反應中可在24小時反應時間後形成41% 1-(甲苯-4-磺醯基)-2,5-二氫-1H-吡咯。當在相同條件下再反應時,轉換率非常低(<3%),僅獲得不足1%之1-(甲苯-4-磺醯基)-2,5-二氫-1H-吡咯且即使在一較高的反應溫度(110℃,在甲苯中)下,該觸媒的活性仍較差。
因此,本發明之目的係獲得優良的置換反應觸媒。
令人驚奇地發現,在氮原子α位置之取代可顯著改良觸媒的活性。
可見,式I之釕複合物具有成為置換反應(例如閉環置換反應或交叉置換反應)中之有用觸媒之潛力。
本發明化合物之特徵在於下式
其中,L係中性配體;X1
及X2
彼此獨立地係陰離子配體;R1
係C1-6
-烷基、鹵素-C1-6
-烷基、C1-6
-烷氧基、C1-6
-烷基羰基、芳基、羥基、芳氧基、硝基、胺基、單-C1-6
-烷基-或二-C1-6
-烷基胺基、鹵素、硫基、C1-6
-烷硫基或SO2
-C1-6
-烷基、SO2
-芳基、SO3
H、SO3
-C1-6
-烷基或OSi(C1-6
-烷基)3
及SO2
-NR'
R",其中R'及R"彼此獨立地係氫或C1-6
-烷基或R'及R"與N原子共同形成碳環;R2
、R3
、R4
、R5
及R6
彼此獨立地係氫、C1-6
-烷基、鹵素-C1-6
-烷基、C1-6
-烷氧基、C1-6
-烷基羰基、芳基、羥基、芳氧基、硝基、胺基、單-C1-6
-烷基-或二-C1-6
-烷基胺基、鹵素、硫基、C1-6
-烷硫基或SO2
-C1-6
-烷基、SO2
-芳基、SO3
H、SO3
-C1-6
-烷基或OSi(C1-6
-烷基)3
及SO2
-NR'
R",其中R'
及R"彼此獨立地係氫或C1-6
-或R'
及R"與N原子共同形成碳環;Y係氫、C1-6
-烷基、C2-6
-烯基或芳基、或Y與R6
共同形成(CH=CR)-或-(CH2
)n
-橋,n係2或3且R如對R2
之定義。
本發明進一步包括一種製備式I化合物之方法及其在置換反應中之用途。
本文中給出以下定義來闡釋及定義用於闡述本發明中各術語的含義及範圍。
術語"烷基"單獨或與其他基團結合使用時,係指含有1至6個碳原子、較佳地1至4個碳原子之具支鏈或直鏈單價飽和脂肪族烴基。該術語藉助諸如甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、1-金鋼烷基等基團及本文特別舉例說明之基團進一步舉例說明。
術語"烯基"單獨或與其他基團結合使用時,係指含有2至6個碳原子、較佳地2至4個碳原子之具支鏈或直鏈單價不飽和脂肪族烴基。該術語藉助諸如乙烯基及丙烯基、丁烯基、戊烯基及己烯基及其同分異構體等基團進一步舉例說明。較佳的烯基基團係乙烯基。
術語"鹵素"係指氟、氯、溴及碘。較佳的鹵素係氯。
術語"鹵素-C1-6
-烷基"係指經鹵素取代之C1-6
-烷基基團,其中鹵素具有如上文之含義。較佳的"鹵素-C1-6
-烷基"基團係氟化C1-6
-烷基基團,例如CF3
、CH2
CF3
、CH(CF3
)2
、C4
F9
。
術語"烷氧基"係指含有1至6個、較佳1至4個連接至氧原子的碳原子之具支鏈或直鏈單價飽和脂肪族烴基。"烷氧基"之實例係甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基及己氧基。較佳者係本文特別舉例說明之烷氧基基團。
烷氧基基團之烷基鏈可視需要經取代,具體而言,經如上文定義之烷氧基基團(較佳為甲氧基或乙氧基)或經芳基基團(較佳為苯基)單取代、二取代或三取代。較佳的經取代烷氧基基團係苄氧基基團。
術語"烷基羰基"係指C1-6
-烷基羰基基團,較佳地係指C1-4
-烷基羰基基團。其包括(例如)乙醯基、丙醯基、丁醯基或新戊醯基。較佳的烷基羰基基團係乙醯基。
術語"烷硫基"係指基團R'
-S-,其中,R'
係C1-6
-烷基,較佳為C1-4
-烷基,例如甲硫基或乙硫基。較佳者係本文特別舉例說明之烷硫基基團。
術語"SO2
-C1-6
-烷基"係指經磺醯基取代之C1-6
-烷基基團。較佳的SO2
-C1-6
-烷基基團係SO2
-甲基。
術語"SO2
-芳基"係指經磺醯基取代之芳基基團。較佳的SO2
-芳基基團係SO2
-苯基。
術語"SO2
-N R'
R"係指經磺醯基取代之胺基基團N R'
R",其中R'
及R"彼此獨立地係氫或C1-6
-烷基或R'
及R"與N原子共同形成碳環。較佳的SO2
-N R'
R"基團係SO2
-N(甲基)2
。
術語"OSi(C1-6
-烷基)3
"係指經三-C1-6
-烷基-取代之甲矽烷氧基基團。OSi(C1-6
-烷基)3
之較佳含義係三甲基甲矽烷氧基、三乙基甲矽烷氧基及第三丁基二甲基甲矽烷氧基。
術語"單-或二-烷基-胺基"係指經C1-6
-烷基(較佳地,C1-4
-烷基)單-或二-取代之胺基基團。單-C1-6
-烷基-胺基基團包括(例如)甲基胺基或乙基胺基。術語"二-C1-6
-烷基-胺基"包括(例如)二甲基胺基、二乙基胺基或乙基甲基胺基。較佳者係本文特別舉例說明之單-或二-C1-4
-烷基胺基基團。因此,應瞭解,術語"二-C1-6
-烷基-胺基"包括環系統,其中兩個烷基基團與其所連接之氮原子共同形成4至7元雜環,其亦可帶有另一選自氮、氧或硫之雜原子。
術語"胺基"及"單-或二-烷基-胺基"亦包括式-NR'
R"H+
Z-
之基團,其中R'
及R"係如上述且Z-係陰離子,例如鹵化物(尤其氯化物)或磺酸鹽(尤其甲烷磺酸鹽或對-甲苯磺酸鹽)。
術語"環烷基"表示含有3至7個碳原子之"C3-7
-環烷基"基團,例如環丙基、環丁基、環戊基、環己基或環庚基。
術語"芳基"涉及苯基或萘基基團,較佳為苯基基團,其可視需要經鹵素、羥基、CN、CF3
、NO2
、NH2
、N(H,烷基)、N(烷基)2
、羧基、胺基羰基、烷基、烷氧基、烷基羰基、SO2
-烷基、SO2
-芳基、SO3
H、SO3
-烷基、SO2
-NR'
R"、芳基及/或芳氧基單-、二-、三-或多-取代。較佳的芳基基團係苯基。
術語"芳氧基"涉及結合至氧原子之芳基基團。術語"芳基"具有如上文定義之含義。較佳的芳氧基基團係苯氧基。
術語"雜芳基"涉及環中含有1至3個雜原子且其餘原子為碳原子之雜環芳基基團。適宜的雜原子包括(但不限於)氧、硫及氮。實例性雜芳基基團包括呋喃基、噻吩基、吡啶基、吡咯基、N-烷基吡咯、嘧啶基、吡嗪基、咪唑基、苯并呋喃基、喹啉基及吲哚基。如同芳基基團,雜芳基基團可視需要經鹵素、羥基、CN、CF3
、NO2
、NH2
、N(H,烷基)、N(烷基)2
、羧基、胺基羰基、烷基、烷氧基、烷基羰基、SO2
-烷基、SO2
-芳基、SO3
H、SO3
-烷基、SO2
-NR'
R"、芳基及/或芳氧基單-、二-、三-或多-取代。
配體L係中性配體,較佳地選自-P(R10
)3
:
其中,R7
及R8
彼此獨立地係C1-6
-烷基、芳基、C2-6
-烯基或1-金鋼烷基且R9a-d
彼此獨立地係氫、C1-6
-烷基、C2-6
-烯基或芳基、或取R9b
及R9c
或R9a
及R9d
共同形成-(CH2
)4
-橋;R10
彼此獨立地係C1-6
-烷基、C3-7
-環烷基、芳基或雜芳基。
在一較佳實施例中,R7
及R8
係C1-6
-烷基或苯基基團,其經C1-6
-烷基二-或三-取代。
更佳地,R7
及R8
係第三丁基、1-金鋼烷基、異丙基、2,6-二異丙基苯基或2,4,6-三甲基苯基,最佳係2,4,6-三甲基苯基。
在一較佳實施例中,R9a
及R9c
係甲基或苯基且R9b
及R9d
係氫或R9a
及R9c
或R9b
及R9d
共同形成-(CH2
)n
-橋,其中n係5或6。因此,應瞭解,若存在對掌性碳原子,則包括外消旋及對映體純淨形式兩者。
在另一較佳實施例中,R9a-d
係氫。
在又一較佳實施例中,L係
其中R7
及R8
係如上文所述。
在另一較佳實施例中,R10
係環己基。
作為陰離子配體X1
及X2
,可選擇鹵化物離子或擬鹵化物離子,例如氰化物離子、羅丹寧(rhodanide)、氰酸根、異氰酸根、乙酸根或三氟乙酸根。對X1
及X2
而言,較佳的陰離子配體係鹵化物離子,而氯離子係最佳的陰離子配體。
在另一較佳實施例中,R1
係C1-6
-烷基、鹵素-C1-6
-烷基或芳基。更佳地,R1
係甲基、三氟甲基、苯基、鄰-甲苯基或2,6-二甲基苯基。
在又一較佳實施例中,R2
、R4
、R5
及R6
係氫。
較佳地,R3
係氫、羥基、C1-6
-烷氧基、C1
-6
-烷氧基羰基、硝基、腔基及鹵素。更佳的R3
代表氯、羥基、苄氧基、胺基、硝基及乙醯基。
以下化合物係本發明之最佳代表。
縮寫:ImH2
Mes=1,3-雙-(2,4,6-三甲基苯基)-2-亞咪唑啶基;ImMes=1,3-雙-(2,4,6-三甲基苯基)-2-亞咪唑基
試驗觸媒之表格:
本發明亦包括製備式I化合物之方法,其包括用式IV化合物
其中R1
至R6
具有如上文之含義。
轉換式III之Ru-前體化合物
其中X1
及X2
係如文中所定義,Cy係環己基且Ph係苯基。
轉化通常在一銅鹽(較佳係氯化銅)存在下、於約0℃至60℃溫度下在有機溶劑例如甲苯、苯、四氫呋喃或二氯甲烷中發生。
式IV化合物可藉由若干習知交叉偶合反應(例如F.Diederich及P.J.Stang在`Metal-catalyzed cross-coupling reactions` Wiley-VCH,1998或J.March在`Advanced organic chemistry ` Wiley-VCH,1992中所述)從可購得或易得之式V化合物與例如乙烯基錫烷、乙烯、硼酸乙烯酯、乙烯基硼烷、乙烯基格氏(Grignard)試劑開始製備或從可購得之式VI醛開始在魏悌希(Wittig)、魏悌希-霍納(Wittig-Horner)、魏悌希-霍納-埃蒙斯(Wittig-Horner-Emmons)、苔彼(Tebbe)或彼得森(Peterson)條件下製備。
本發明之化合物可用於置換反應,具體而言用於閉環置換反應或交叉置換反應中。儘管熟習此項技術者瞭解應使反應條件適應每個底物,但通常可應用以下條件。
閉環置換反應及交叉置換反應通常在惰性有機溶劑例如在甲苯、二甲苯、三甲苯及二氯甲烷中且在20℃至180℃之反應溫度下進行。觸媒濃度一般選在0.1莫耳%與10莫耳%之間。
以下實例用於闡釋而非限制本發明。
縮寫:ImH2
Mes=1,3-雙-(2,4,6-三甲基苯基)-2-亞咪唑啶基;ImMes=1,3-雙-(2,4,6-三甲基苯基)-2-亞咪唑基
試驗觸媒之表格:
將500毫克(0.59毫莫耳)[RuCl2
(PCy3
)(ImH2
Mcs)(苯基亞甲基)](購自Sigma-Aldrich公司,St.Louis,USA)、60毫克(0.61毫莫耳)氯化銅及100毫克(0.64毫莫耳)8-乙烯基喹啉(根據G.T.Crisp,S.Papadopoulos,Aust.J.Chem.1989,42,279-285製備)存於40毫升二氯甲烷中之懸浮液在室溫下攪拌90分鐘。將反應混合物蒸發至乾燥且將分離出的粗產物藉由矽膠層析法(己烷/乙酸乙酯2:1)純化產生255毫克(70%)綠色晶體狀標題化合物。MS:584.4(M-Cl+
).1
H-NMR(300MHz,CD2
Cl2
):2.36(s,6H);2.40(s,12H);4.04(s,4H);7.01(s,4H);7.19(dd,J=8.4,4.9Hz,1H);7.34(t,J=7.7Hz,1H);7.51(d,J=7.1Hz,1H);8.08-8.18(m,2H);8.26(dd,J=4.8,1.3Hz,1H);16.95(s,1H).C31
H33
N3
Cl2
Ru之分析計算值:C,60.09;H,5.37;N,6.78;Cl,11.44。實驗值:C,60.06;H,5.75;N,6.16;Cl,10.90。
實例2 4-氯-2-三氟甲基-8-乙烯基-喹啉
將2.00克(6.25毫莫耳)8-溴-4-氯-2-三氟甲基喹啉(購自Maybridge,Cornwall,UK)、258毫克(0.31毫莫耳)PdCl2
dppf.
CH2
Cl2
、1.29克(9.37毫莫耳)乙烯基四氟硼酸鉀及0.88毫升(6.28毫莫耳)三乙基胺存於40毫升乙醇中之懸浮液加熱回流3小時。將所得到的黃色懸浮液過濾且將濾液蒸發至乾燥。將殘留物懸浮在乙酸乙酯中、過濾且濾液用水萃取。將有機層蒸發至乾燥且將分離出的粗產物藉由矽膠層析法(己烷)純化產生1.17克(72%)白色晶體狀標題化合物。MS:257.1(M+
).1
H-NMR(300 MHz,CDCl3
):5.58(dd,J=11.1,1.1Hz,1H);6.07(dd,J=17.8,1.1Hz,1H);7.75(t,J=7.7Hz,1H);7.81(s,1H);7.99(dd,J=17.8,11.1Hz,1H);8.09(d,J=7.2Hz,1H);8.23(d,J=8.4Hz,1H)。
實例3[RuCl 2 (ImH 2 Mes)((4-氯-2-三氟甲基-8-喹啉基)亞甲基)]
將1.39克(1.64毫莫耳)[RuCl2
(PCy3
)(ImH2
Mes)(苯基亞甲基)]、0.17克(1.80毫莫耳)氯化銅及464毫克(1.69毫莫耳)4-氯-2-三氟甲基-8-乙烯基-喹啉存於100毫升二氯甲烷中之懸浮液在30℃下攪拌90分鐘。將反應混合物蒸發至乾燥且將分離出的粗產物藉由矽膠層析法(己烷/乙酸乙酯5:2)純化產生278毫克(24%)綠色晶體狀標題化合物。MS:721.2(M+
).1
H-NMR(300 MHz,CD2
Cl2
):2.85(s,6H);2.40(s,12H);4.05(s,4H);7.01(s,4H);7.54(s,1H);7.56(t,J=7.7Hz,1H);7.65(d,J=6.8Hz,1H);8.51(d,J=8.4Hz,1H);16.70-17.10(br,1H)。
實例4 2-苯基-8-乙烯基-喹啉-4-酚
將500毫克(1.67毫莫耳)8-溴-2-苯基-喹啉-4-酚(購自Ubichem Research有限公司,Budapest,Hungary)、97毫克(0.09毫莫耳)Pd(PPh3
)4
、71毫克(1.67毫莫耳)氯化鋰及528毫克(1.67毫莫耳)三丁基乙烯基錫烷存於20毫升二氧雜環己烷中之懸浮液在90℃下加熱16小時。將所得到的黃色懸浮液過濾且將濾液蒸發至乾燥。將殘留物懸浮在乙酸乙酯中、過濾且濾液用水萃取。將有機層蒸發至乾燥且將分離出的粗產物藉由矽膠層析法(乙酸乙酯)純化產生178毫克(43%)微黃色晶體狀標題化合物。1
H-NMR(300MHz,CDCl3
):5.59(d,J=11.1Hz,1H);5.75(d,J=17.4Hz,1H);6.42(s,1H);7.04(dd,J=17.4,11.1Hz,1H);7.23(t,J=8.1Hz,1H);7.40-7.60(m,6H);8.21(d,J=8.1Hz,1H);8.70(br,1H)。
實例5[RuCl 2 (ImH 2 Mes)((4-羥基-2-苯基-8-喹啉基)亞甲基)]
將100毫克(0.12毫莫耳)[RuCl2
(PCy3
)(ImH2
Mes)(苯基亞甲基)]、12毫克(0.12毫莫耳)氯化銅及100毫克(0.12毫莫耳)2-苯基-8-乙烯基-喹啉-4-酚存於11毫升二氯甲烷中之懸浮液在40℃下攪拌1小時。將反應混合物蒸發至乾燥且將分離出的粗產物藉由矽膠層析法(己烷/乙酸乙酯2:1)純化產生51毫克(61%)綠色晶體狀標題化合物。MS:711.1(M+
).1
H-NMR(300 MHz,CD2
Cl2
):2.32(s,12H);2.41(s,6H);3.90(s,4H);6.12-6.28(br,1H);6.80-6.92(m,2H);6.98(s,4H);7.04-7.14(m,1H);7.19(t,J=7.1Hz,1H);7.29(d,J=6.9Hz,1H);7.35(d,J=7.5Hz,2H);7.49(d,J=7.1Hz,1H);7.80-8.00(br,1H);17.34(s,1H)。
實例6 4-氯-8-乙烯基-喹啉
將975毫克(4.02毫莫耳)8-溴-4-氯喹啉(購自Ubichem Research有限公司,Budapest,Hungary)、166毫克(0.20毫莫耳)PdCl2
dppf.
CH2
Cl2
、833毫克(6.00毫莫耳)乙烯基四氟硼酸鉀及0.57毫升(4.10毫莫耳)三乙基胺存於20毫升乙醇中之懸浮液加熱回流3小時。將所得到的黃色懸浮液過濾且將濾液蒸發至乾燥。將殘留物懸浮在乙酸乙酯中、過濾且濾液用水萃取。將有機層蒸發至乾燥且將分離出的粗產物藉由矽膠層析法(己烷/乙酸乙酯9:1)純化產生207毫克(27%)白色晶體狀標題化合物。MS:189.1(M+
).1
H-NMR(300 MHz,CDCl3
):5.53(d,J=11.1Hz,1H);5.95(d,J=17.7Hz,1H);7.51(d,J=4.6Hz.1H);7.63(t,J=7.9Hz,1H);7.96(dd,J=17.7,11.1Hz,1H);7.97(d,J=7.1Hz,1H);8.19(d,J=8.5Hz,1H);8.80(d,J=4.6Hz,1H)。
實例7(用於比較)[RuCl 2 (ImH 2 Mes)((4-氯-8-喹啉基)亞甲基)]
將790毫克(0.93毫莫耳)[RuCl2
(PCy3
)(ImH2
Mes)(苯基亞甲基)]、95毫克(0.96毫莫耳)氯化銅及196毫克(1.03毫莫耳)4-氯-8-乙烯基-喹啉存於70毫升二氯甲烷中之懸浮液於30℃下攪拌90分鐘。將反應混合物蒸發至乾燥且將分離出的粗產物藉由矽膠層析法(己烷/乙酸乙酯5:2)純化並最後在室溫下於20毫升戊烷中浸漬30分鐘產生311毫克(51%)綠色晶體狀標題化合物。MS:655.0(M+
).1
H-NMR(300 MHz,CD2
Cl2
):2.35(s,6H);2.39(s,12H);4.04(s,4H);7.00(s,4H);7.25(d,J=5.3Hz,1H);7.43(dd,J=8.2,7.3Hz,1H);7.56(dd,J=7.1,0.7Hz,1H);8.13(d,J=5.3Hz,1H);8.41(dd,J=8.2,0.7Hz,1H);16.95(s,1H)。C31
H32
N3
Cl3
Ru之分析計算值:C,56.93;H,4.93;N,6.42;Cl,16.26。實驗值:C,56.59;H,5.04;N,6.02;Cl,15.49。
實例8 2-甲基-8-乙烯基-喹啉
將4.80克(21.60毫莫耳)8-溴-2-甲基喹啉(購自ACB Block有限公司,Moscow,Russia)、0.89克(1.10毫莫耳)PdCl2
dppf.
CH2
Cl2
、4.48克(32.40毫莫耳)乙烯基四氟硼酸鉀及3.10毫升(22.10毫莫耳)三乙基胺存於150毫升乙醇中之懸浮液加熱回流3小時。將所得到的黃色懸浮液過濾且將濾液蒸發至乾燥。將殘留物懸浮在乙酸乙酯中、過濾且濾液用水萃取。將有機層蒸發至乾燥且將分離出的粗產物藉由矽膠層析法(CH2
Cl2
/乙酸乙酯98:2)純化產生2.68克(73%)無色油狀標題化合物。MS:169.1(M+
).1
H-NMR(300 MHz,CDCl3
):2.74(s,1H);5.47(dd,J=11.1,1.6Hz,1H);5.97(dd,17.9,1.6Hz,1H);7.24(d,J=8.4Hz,1H);7.43(t,J=7.7Hz,1H);7.66(dd,J=8.1,1.2Hz,1H);7.87(dd,J=7.3、1.2Hz,1H);7.97(d,J=8.4Hz,1H);8.05(dd,J=17.9,11.1Hz,1H)。
實例9[RuCl 2 (ImH 2 Mes)((2-甲基-8-喹啉基)亞甲基)]
將218毫克(0.26毫莫耳)[RuCl2
(PCy3
)(ImH2
Mes)(苯基亞甲基)]、26毫克(0.26毫莫耳)氯化銅及49毫克(0.29毫莫耳)2-甲基-8-乙烯基-喹啉存於17毫升二氯甲烷中之懸浮液在30℃下攪拌90分鐘。將反應混合物蒸發至乾燥且將分離出的粗產物藉由矽膠層析法(己烷/乙酸乙酯7:3)純化並最後在室溫下於15毫升己烷中浸漬30分鐘產生157毫克(96%)綠色晶體狀標題化合物。MS:632.9(M+
).1
H-NMR(300 MHz,C6
D6
):2.15(s,3H);2.29(s,6H);2.64(s,12H);3.49(s,4H);6.30(d,J=8.4Hz,1H);6.80(t,J=7.3Hz,1H);6.98(s,4H);7.10(d,J=8.4Hz,1H);7.40(d,J=8.1Hz,1H);7.52(d,J=7.0Hz,1H),17.15-17.32(br,1H).C32
H35
N3
Cl2
Ru之分析計算值:C,60.66;H,5.57;N,6.63;Cl,11.19。實驗值:C,60.33;H,5.58;N,6.27;Cl,10.90。
實例10[RuCl 2 (三環己基膦)((4-氯-2-三氟甲基-8-喹啉基)亞甲基)]
將3.07克(3.73毫莫耳)[RuCl2
(PCy3
)2
(苯基亞甲基)](購自Sigma-Aldrich公司,St.Louis,USA)、380毫克(3.84毫莫耳)氯化銅及1.06克(4.10毫莫耳)4-氯-2-三氟甲基-8-乙烯基-喹啉存於135毫升二氯甲烷中之懸浮液在30℃下攪拌90分鐘。將反應混合物蒸發至乾燥且將分離出的粗產物藉由矽膠層析法(己烷/乙酸乙酯2:1)純化並最後在室溫下於50毫升戊烷中浸漬30分鐘產生429毫克(17%)暗綠色晶體狀標題化合物。MS:697.0(M+
).31
P-NMR(121 MHz,C6
D6
):54.2 ppm.1
H-NMR(300 MHz,C6
D6
):1.18-2.35(m,30H);2.60(q,J=12.0Hz,3H);6.82(t,J=6.0Hz,1H);7.01(d,J=3.0Hz,1H);7.55(d,J=6.0Hz,1H);7.89(d,J=6.0Hz,1H);17.80-17.90(m,1H)。
實例11[RuCl 2 (ImMes)((4-氯-2-三氟甲基-8-喹啉基)亞甲基)]
將1.30克(1.54毫莫耳)[RuCl2
(PCy3
)(ImMes)(苯基亞甲基)](根據J.Huang,E.Stevens,S.Nolan,J.Petersen,J.Am.Chem.Soc.1999,121,2674-2678製備)、0.15克(1.54毫莫耳)氯化銅及435毫克(1.68毫莫耳)4-氯-2-三氟甲基-8-乙烯基-喹啉存於100毫升二氯甲烷中之懸浮液在30℃下攪拌90分鐘。將反應混合物蒸發至乾燥且將分離出的粗產物藉由矽膠層析法(己烷/乙酸乙酯5:2)純化產生260毫克(24%)橙色晶體狀標題化合物。MS:719.0(M+
).1
H-NMR(300 MHz,C6
D6
):2.33(s,6H);2.46(s,12H);6.30(s,2H);6.76(dd,J=9.0,6.0Hz,1H);6.83(s,1H);6.97(s,4H);7.58(d,J=6.0Hz,1H);7.85(d,J=9.0Hz,1H);17.31-17.36(m,1H)。
實例12 1-(甲苯-4-磺醯基)-2,5-二氫-1H-吡咯
在110℃下攪拌257毫克(1.02毫莫耳)N,N-二烯丙基-4-甲基苯磺醯胺(根據S.Varray,R.Lazaro.,J.Matinez,F.Lamaty,Organometallics 2003,22,2426-2435製備)及19毫克(0.03毫莫耳)[RuCl2
(ImH2
Mes)((4-氯-2-三氟甲基-8-喹啉基)亞甲基)]存於5毫升甲苯中之溶液。為監測轉化率及選擇性,1小時及4小時後取0.2毫升樣品。每份樣品皆經矽膠墊過濾,將濾液蒸發至乾燥並藉助GC(管柱:DB-1701;注射器:260℃;檢測器:260℃;烘箱:70至250℃/5℃/分鐘;載氣:H2
(60千帕);滯留時間:15.5分鐘N,N-二烯丙基-4-甲基苯磺醯胺、24.5分鐘1-(甲苯-4-磺醯基)-2,3-二氫-1H-吡咯、25.5分鐘1-(甲苯-4-磺醯基)-2,5-二氫-1H-吡咯)進行分析。1小時後(98%轉化率),形成96%之標題化合物及2%之1-(甲苯-4-磺醯基)-2,3-二氫-1H-吡咯且4小時後(100%轉化率)形成92%之標題化合物及8%之1-(甲苯-4-磺醯基)-2,3-二氫-1H-吡咯。1-(甲苯-4-磺醯基)-2,5-二氫-1H-吡咯之1
H-NMR譜(300 MHz,C6
D6
):2.43(s,3H);4.12(s,4H);5.65(s,2H);7.32(d,J=8.3Hz,2H);7.73(d,J=8.3Hz,2H)。1-(甲苯-4-磺醯基)-2,3-二氫-1H-吡咯之1
H-NMR譜(300 MHz,C6
D6
):2.40-2.55(m,2H);2.43(s,3H);3.48(t,J=8.9Hz,2H);5.10-5.15(m,1H);8.35-8.40(m,1H);7.32(d,J=8.3Hz,2H);7.67(d,J=8.3Hz,2H)。
實例13(用於比較)1-(甲苯-4-磺醯基)-2,5-二氫-1H-吡咯
以與實例12類似的方式,但在17毫克(0.03毫莫耳)[RuCl2
(ImH2
Mes)((4-氯-8-喹啉基)亞甲基)]存在下而非[RuCl2
(ImH2
Mes)((4-氯-2-三氟甲基-8-喹啉基)亞甲基)]作為觸媒,1小時後(7%轉化率)形成7%之標題化合物且4小時後(15%轉化率)形成14%之標題化合物及1%之1-(甲苯-4-磺醯基)-2,3-二氫-1H-吡咯。
實例14(用於吡較)1-(甲苯-4-磺醯基)-2,5-二氫-1H-吡咯
a)以與實例12類似的方式,但在16毫克(0.03毫莫耳)[RuCl2
(ImH2
Mes)(8-喹啉基亞甲基)]存在下而非[RuCl2
(ImH2
Mes)((4-氯-2-三氟甲基-8-喹啉基)亞甲基)]作為觸媒,1小時後(7%轉化率)形成7%之標題化合物且4小時後(31%轉化率)形成28%之標題化合物及3%之1-(甲苯-4-磺醯基)-2,3-二氫-1H-吡咯。
b)根據Barbasiewicz等人,(Organometallics,2006年6月17日於萬維網上發表)所述,在室溫下攪拌88毫克(0.35毫莫耳)N,N-二烯丙基-4-甲基苯磺醯胺及11.2毫克(0.018毫莫耳)[RuCl2
(ImH2
Mes)(8-喹啉基亞甲基)]存於17.5毫升二氯甲烷中之溶液。為監測轉化率及選擇性,4小時及24小時後取0.2毫升樣品。每份樣品經矽膠墊過濾,將濾液蒸發至乾燥並藉助GC進行分析,如實例12中所述。4小時後(2%轉化率)形成0.6%之標題化合物及0.3%之1-(甲苯-4-磺醯基)-2,3-二氫-1H-吡咯且24小時後(3%轉化率)形成1.5%之標題化合物及0.5%之1-(甲苯-4-磺醯基)-2,3-二氫-1H-吡咯。
實例15 1-(甲苯-4-磺醯基)-2,5-二氫-1H-吡咯
以與實例12類似的方式,但在18毫克(0.03毫莫耳)[RuCl2
(ImH2
Mes)((4-羥基-2-苯基-8-喹啉基)亞甲基)]存在下而非[RuCl2
(ImH2
Mes)((4-氯-2-三氟甲基-8-喹啉基)亞甲基)]作為觸媒,1小時後(99%轉化率)形成98%之標題化合物及1%之1-(甲苯-4-磺醯基)-2,3-二氫-1H-吡咯且4小時後(100%轉化率)形成99%之標題化合物及1%之1-(甲苯-4-磺醯基)-2,3-二氫-1H-吡咯。
實例16 1-(甲苯-4-磺醯基)-2,5-二氫-1H-吡咯
以與實例12類似的方式,但在18毫克(0.03毫莫耳)[RuCl2
(ImH2
Mes)((2-甲基-8-喹啉基)亞甲基)]存在下而非[RuCl2
(ImH2
Mes)((4-氯-2-三氟甲基-8-喹啉基)亞甲基)]作為觸媒,1小時後(22%轉化率)形成11%之標題化合物且4小時後(66%轉化率)形成22%之標題化合物及5%之1-(甲苯-4-磺醯基)-2,3-二氫-1H-吡咯。
實例17 1-(甲苯-4-磺醯基)-2,5-二氫-1H-吡咯
以與實例12類似的方式,但在16毫克(0.03毫莫耳)[RuCl2
(三環己基膦)((4-氯-2-三氟甲基-8-喹啉基)亞甲基)]存在下而非[RuCl2
(ImH2
Mes)((4-氯-2-三氟甲基-8-喹啉基)亞甲基)]作為觸媒,1小時後(11%轉化率)形成7%之標題化合物及1%之1-(甲苯-4-磺醯基)-2,3-二氫-1H-吡咯且4小時後(42%轉化率)形成25%之標題化合物及1%之1-(甲苯-4-磺醯基)-2,3-二氫-1H-吡咯。
實例18 1-(甲苯-4-磺醯基)-2,5-二氫-1H-吡咯
以與實例12類似的方式,但在20毫克(0.03毫莫耳)[RuCl2
(ImMes)((4-氯-2-三氟甲基-8-喹啉基)亞甲基)]存在下而非[RuCl2
(ImH2
Mes)((4-氯-2-三氟甲基-8-喹啉基)亞甲基)]作為觸媒,1小時後(53%轉化率)形成11%之標題化合物及11%之1-(甲苯-4-磺醯基)-2,3-二氫-1H-吡咯,4小時後(100%轉化率)形成54%之標題化合物及2%之1-(甲苯-4-磺醯基)-2,3-二氫-1H-吡咯且20小時後(100%轉化率)形成1%之標題化合物及64%之1-(甲苯-4-磺醯基)-2,3-二氫-1H-吡咯。
實例19(E)/(Z)-2-[3-氰基-2-丙烯基]丙二酸二乙酯
在110℃下攪拌100.0毫克(0.48毫莫耳)烯丙基丙二酸二乙酯、77.4毫克(1.45毫莫耳)丙烯腈及35.0毫克(0.05毫莫耳)[RuCl2
(ImH2
Mes)((4-氯-2-三氟甲基-8-喹啉基)亞甲基)]存於5毫升甲苯中之溶液。為監測轉化率及選擇性,在3小時及40小時後取0.05毫升樣品。每份樣品皆經矽膠墊過濾,將濾液蒸發至乾燥並藉助GC(管柱:HP-5,5%苯基甲基矽氧烷(Agilent 19091-413);注射器:250℃;檢測器:250℃;烘箱:100至150℃/5℃/分鐘,150℃下5分鐘,150至200℃/5℃/分鐘及200至300℃/20℃/分鐘;載氣:He(0.46巴);滯留時間:9.2分鐘烯丙基丙二酸二乙酯、17.5分鐘(Z)-2-[3-氰基-2-丙烯基]丙二酸二乙酯及18.8分鐘(E)-2-[3-氰基-2-丙烯基]丙二酸二乙酯)進行分析。3小時後(66%轉化率)形成57%之標題化合物且40小時後(94%轉化率)形成83%之標題化合物(呈(E):(Z)1:2混合物形式)。在低壓下蒸發溶劑後,將粗產物藉由矽膠層析法(環己烷/乙酸乙酯8:2)純化產生65.1毫克(60%)之標題化合物(呈(E):(Z)1:2混合物形式)。MS:226.3(M+
)。2-[3-氰基-2-丙烯基]丙二酸二乙酯之1
H-NMR譜(300 MHz,C6
D6
):(Z)-同分異構體:1.29(t,J=7.1Hz,6H);2.99(td,J=7.1,1.5Hz,2H);3.51(t,J=7.0Hz,1H);4.20-4.24(m,4H);5.40-5.42(m,1H);6.54(m,1H)。(E)-同分異構體:1.28(t,J=7.1Hz,6H);2.79(td,J=7.1,1.5Hz,2H);3.46(t,J=7.1Hz,1H);4.20-4.24(m,4H);5.40-5.42(m,1H);6.68(m,1H)。
實例20(E)/(Z)-2-[3-氰基-2-丙烯基]丙二酸二乙酯
以與實例19類似的方式,但在34.9毫克(0.05毫莫耳)[RuCl2
(ImMes)((4-氯-2-三氟甲基-8-喹啉基)亞甲基)]存在下而非[RuCl2
(ImH2
Mes)((4-氯-2-三氟甲基-8-喹啉基)亞甲基)]作為觸媒,19小時後(80%轉化率)形成48%之標題化合物且40小時後(87%轉化率)形成49%之標題化合物,其呈(E):(Z)1:2混合物形式。
Claims (7)
- 一種式I化合物,
- 如請求項1之化合物,其中,X1 及X2 係氯。
- 如請求項1之化合物,其中,R1 係甲基、三氟甲基或苯基。
- 一種製備如請求項1至3之式I化合物之方法,其包括用式IV化合物轉換下式之釕-前體化合物
- 一種如請求項1至3中任一項之式I化合物在置換反應中之用途。
- 如請求項5之式I化合物之用途,其係用於閉環置換反應中。
- 如請求項5之式I化合物之用途,其係用於交叉置換反應中。
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