JP5284269B2 - ルテニウムを主成分とした触媒錯体、およびオレフィンメタセシスのための前記錯体の使用 - Google Patents
ルテニウムを主成分とした触媒錯体、およびオレフィンメタセシスのための前記錯体の使用 Download PDFInfo
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- JP5284269B2 JP5284269B2 JP2009538722A JP2009538722A JP5284269B2 JP 5284269 B2 JP5284269 B2 JP 5284269B2 JP 2009538722 A JP2009538722 A JP 2009538722A JP 2009538722 A JP2009538722 A JP 2009538722A JP 5284269 B2 JP5284269 B2 JP 5284269B2
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- 239000003054 catalyst Substances 0.000 title description 33
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title description 8
- 229910052707 ruthenium Inorganic materials 0.000 title description 8
- 238000005865 alkene metathesis reaction Methods 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 claims description 56
- -1 that is Chemical class 0.000 claims description 30
- 239000003446 ligand Substances 0.000 claims description 24
- 150000001408 amides Chemical class 0.000 claims description 18
- 239000000460 chlorine Substances 0.000 claims description 13
- NJNNQEXHOIGLJK-UHFFFAOYSA-N 3-ethenyl-4-propan-2-yloxyaniline Chemical compound CC(C)OC1=CC=C(N)C=C1C=C NJNNQEXHOIGLJK-UHFFFAOYSA-N 0.000 claims description 12
- 239000012041 precatalyst Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 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 3
- 239000003550 marker Substances 0.000 claims description 3
- 229910017008 AsF 6 Inorganic materials 0.000 claims description 2
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910018286 SbF 6 Inorganic materials 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229940063013 borate ion Drugs 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- GJVFBWCTGUSGDD-UHFFFAOYSA-L pentamethonium bromide Chemical compound [Br-].[Br-].C[N+](C)(C)CCCCC[N+](C)(C)C GJVFBWCTGUSGDD-UHFFFAOYSA-L 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 22
- 238000003786 synthesis reaction Methods 0.000 description 22
- 239000012327 Ruthenium complex Substances 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 239000000741 silica gel Substances 0.000 description 17
- 229910002027 silica gel Inorganic materials 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 238000004587 chromatography analysis Methods 0.000 description 13
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 238000007429 general method Methods 0.000 description 12
- 238000005649 metathesis reaction Methods 0.000 description 10
- 0 C*1ccccc1 Chemical compound C*1ccccc1 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 8
- 238000010828 elution Methods 0.000 description 8
- 239000003480 eluent Substances 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 239000012429 reaction media Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003303 ruthenium Chemical class 0.000 description 4
- VRBHURBJIHILRI-UHFFFAOYSA-N 1H-inden-1-ylidene Chemical group C1=CC=C2[C]C=CC2=C1 VRBHURBJIHILRI-UHFFFAOYSA-N 0.000 description 3
- VNDFYDZORAPFSA-UHFFFAOYSA-N 2-(2-phenylethenoxy)ethenylbenzene Chemical compound C=1C=CC=CC=1C=COC=CC1=CC=CC=C1 VNDFYDZORAPFSA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- FCDPQMAOJARMTG-UHFFFAOYSA-M benzylidene-[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-dichlororuthenium;tricyclohexylphosphanium Chemical compound C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=[Ru](Cl)(Cl)=CC1=CC=CC=C1 FCDPQMAOJARMTG-UHFFFAOYSA-M 0.000 description 3
- 238000010668 complexation reaction Methods 0.000 description 3
- JCYWCSGERIELPG-UHFFFAOYSA-N imes Chemical compound CC1=CC(C)=CC(C)=C1N1C=CN(C=2C(=CC(C)=CC=2C)C)[C]1 JCYWCSGERIELPG-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- IUYZPYVWJWHHFD-UHFFFAOYSA-N n-(3-ethenyl-4-propan-2-yloxyphenyl)-2,2,2-trifluoroacetamide Chemical compound CC(C)OC1=CC=C(NC(=O)C(F)(F)F)C=C1C=C IUYZPYVWJWHHFD-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- LSMWOQFDLBIYPM-UHFFFAOYSA-N 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-2h-imidazol-1-ium-2-ide Chemical compound CC1=CC(C)=CC(C)=C1N1[C-]=[N+](C=2C(=CC(C)=CC=2C)C)CC1 LSMWOQFDLBIYPM-UHFFFAOYSA-N 0.000 description 2
- NRKYWOKHZRQRJR-UHFFFAOYSA-N 2,2,2-trifluoroacetamide Chemical compound NC(=O)C(F)(F)F NRKYWOKHZRQRJR-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000008094 contradictory effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- MFGJWGZXHCDWLT-UHFFFAOYSA-N n-(3-ethenyl-4-propan-2-yloxyphenyl)-2,3,4,5,6-pentafluorobenzamide Chemical compound C1=C(C=C)C(OC(C)C)=CC=C1NC(=O)C1=C(F)C(F)=C(F)C(F)=C1F MFGJWGZXHCDWLT-UHFFFAOYSA-N 0.000 description 2
- FSHNMTMNNCZFID-UHFFFAOYSA-N n-(3-ethenyl-4-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC=C(NC(C)=O)C=C1C=C FSHNMTMNNCZFID-UHFFFAOYSA-N 0.000 description 2
- YRCHYHRCBXNYNU-UHFFFAOYSA-N n-[[3-fluoro-4-[2-[5-[(2-methoxyethylamino)methyl]pyridin-2-yl]thieno[3,2-b]pyridin-7-yl]oxyphenyl]carbamothioyl]-2-(4-fluorophenyl)acetamide Chemical compound N1=CC(CNCCOC)=CC=C1C1=CC2=NC=CC(OC=3C(=CC(NC(=S)NC(=O)CC=4C=CC(F)=CC=4)=CC=3)F)=C2S1 YRCHYHRCBXNYNU-UHFFFAOYSA-N 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 1
- KAFZOLYKKCWUBI-HPMAGDRPSA-N (2s)-2-[[(2s)-2-[[(2s)-1-[(2s)-3-amino-2-[[(2s)-2-[[(2s)-2-(3-cyclohexylpropanoylamino)-4-methylpentanoyl]amino]-5-methylhexanoyl]amino]propanoyl]pyrrolidine-2-carbonyl]amino]-5-(diaminomethylideneamino)pentanoyl]amino]butanediamide Chemical compound N([C@@H](CC(C)C)C(=O)N[C@@H](CCC(C)C)C(=O)N[C@@H](CN)C(=O)N1[C@@H](CCC1)C(=O)N[C@@H](CCCN=C(N)N)C(=O)N[C@@H](CC(N)=O)C(N)=O)C(=O)CCC1CCCCC1 KAFZOLYKKCWUBI-HPMAGDRPSA-N 0.000 description 1
- UXKLQDCALAWFIU-VKNDCNMPSA-N (6r,7r)-1-[(4s,5r)-4-acetyloxy-5-methyl-3-methylidene-6-phenylhexyl]-4,7-dihydroxy-6-tetradecoxy-2,8-dioxabicyclo[3.2.1]octane-3,4,5-tricarboxylic acid Chemical compound C([C@@H](C)[C@H](OC(C)=O)C(=C)CCC12[C@H](O)[C@H](C(O2)(C(O)=O)C(O)(C(O1)C(O)=O)C(O)=O)OCCCCCCCCCCCCCC)C1=CC=CC=C1 UXKLQDCALAWFIU-VKNDCNMPSA-N 0.000 description 1
- VGNCBRNRHXEODV-XXVHXNRLSA-N (6r,7r)-1-[(4s,5r)-4-acetyloxy-5-methyl-3-methylidene-6-phenylhexyl]-6-dodecoxy-4,7-dihydroxy-2,8-dioxabicyclo[3.2.1]octane-3,4,5-tricarboxylic acid Chemical compound C([C@@H](C)[C@H](OC(C)=O)C(=C)CCC12[C@H](O)[C@H](C(O2)(C(O)=O)C(O)(C(O1)C(O)=O)C(O)=O)OCCCCCCCCCCCC)C1=CC=CC=C1 VGNCBRNRHXEODV-XXVHXNRLSA-N 0.000 description 1
- IGVKWAAPMVVTFX-BUHFOSPRSA-N (e)-octadec-5-en-7,9-diynoic acid Chemical compound CCCCCCCCC#CC#C\C=C\CCCC(O)=O IGVKWAAPMVVTFX-BUHFOSPRSA-N 0.000 description 1
- JNPGUXGVLNJQSQ-BGGMYYEUSA-M (e,3r,5s)-7-[4-(4-fluorophenyl)-1,2-di(propan-2-yl)pyrrol-3-yl]-3,5-dihydroxyhept-6-enoate Chemical compound CC(C)N1C(C(C)C)=C(\C=C\[C@@H](O)C[C@@H](O)CC([O-])=O)C(C=2C=CC(F)=CC=2)=C1 JNPGUXGVLNJQSQ-BGGMYYEUSA-M 0.000 description 1
- BHNZEZWIUMJCGF-UHFFFAOYSA-N 1-chloro-1,1-difluoroethane Chemical compound CC(F)(F)Cl BHNZEZWIUMJCGF-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- WPWWHXPRJFDTTJ-UHFFFAOYSA-N 2,3,4,5,6-pentafluorobenzamide Chemical compound NC(=O)C1=C(F)C(F)=C(F)C(F)=C1F WPWWHXPRJFDTTJ-UHFFFAOYSA-N 0.000 description 1
- KVIFXWNDSNHROF-UHFFFAOYSA-N 2-chloro-n-(3-ethenyl-4-propan-2-yloxyphenyl)-2,2-difluoroacetamide Chemical compound CC(C)OC1=CC=C(NC(=O)C(F)(F)Cl)C=C1C=C KVIFXWNDSNHROF-UHFFFAOYSA-N 0.000 description 1
- UTCWESKNHLBRDD-UHFFFAOYSA-N 3-chloro-2,2,3,3-tetrafluoropropanoyl chloride Chemical compound FC(F)(Cl)C(F)(F)C(Cl)=O UTCWESKNHLBRDD-UHFFFAOYSA-N 0.000 description 1
- INUNLMUAPJVRME-UHFFFAOYSA-N 3-chloropropanoyl chloride Chemical compound ClCCC(Cl)=O INUNLMUAPJVRME-UHFFFAOYSA-N 0.000 description 1
- SKDHHIUENRGTHK-UHFFFAOYSA-N 4-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=C(C(Cl)=O)C=C1 SKDHHIUENRGTHK-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- QUMCIHKVKQYNPA-RUZDIDTESA-N C1(CCCCC1)CN1[C@@H](C=2N(C=3C=NC(=NC1=3)NC1=C(C=C(C(=O)NC3CCN(CC3)C)C=C1)OC)C(=NN=2)C)CC Chemical compound C1(CCCCC1)CN1[C@@H](C=2N(C=3C=NC(=NC1=3)NC1=C(C=C(C(=O)NC3CCN(CC3)C)C=C1)OC)C(=NN=2)C)CC QUMCIHKVKQYNPA-RUZDIDTESA-N 0.000 description 1
- PZLNAVZLIGDRMV-UHFFFAOYSA-N CCOC(C(Nc(cc1)cc2c1[O](C(C)C)[U]=C2)=O)=O Chemical compound CCOC(C(Nc(cc1)cc2c1[O](C(C)C)[U]=C2)=O)=O PZLNAVZLIGDRMV-UHFFFAOYSA-N 0.000 description 1
- XJDIOTLSUPJZTA-UHFFFAOYSA-N CSN(CC1)CN1SC Chemical compound CSN(CC1)CN1SC XJDIOTLSUPJZTA-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011984 grubbs catalyst Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- GHCYKINLFBHAHJ-UHFFFAOYSA-N n,n'-bis(3-ethenyl-4-propan-2-yloxyphenyl)oxamide Chemical compound C1=C(C=C)C(OC(C)C)=CC=C1NC(=O)C(=O)NC1=CC=C(OC(C)C)C(C=C)=C1 GHCYKINLFBHAHJ-UHFFFAOYSA-N 0.000 description 1
- VDCVNGOVUXDMBE-UHFFFAOYSA-O n-(3-ethenyl-4-propan-2-yloxyphenyl)-2,2-difluoro-2-(3-methylimidazol-3-ium-1-yl)acetamide Chemical compound C1=C(C=C)C(OC(C)C)=CC=C1NC(=O)C(F)(F)[N+]1=CN(C)C=C1 VDCVNGOVUXDMBE-UHFFFAOYSA-O 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- PFGVNLZDWRZPJW-OPAMFIHVSA-N otamixaban Chemical compound C([C@@H](C(=O)OC)[C@@H](C)NC(=O)C=1C=CC(=CC=1)C=1C=C[N+]([O-])=CC=1)C1=CC=CC(C(N)=N)=C1 PFGVNLZDWRZPJW-OPAMFIHVSA-N 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- MYHOHFDYWMPGJY-UHFFFAOYSA-N pentafluorobenzoyl chloride Chemical compound FC1=C(F)C(F)=C(C(Cl)=O)C(F)=C1F MYHOHFDYWMPGJY-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- JQSHBVHOMNKWFT-DTORHVGOSA-N varenicline Chemical compound C12=CC3=NC=CN=C3C=C2[C@H]2C[C@@H]1CNC2 JQSHBVHOMNKWFT-DTORHVGOSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
-
- C—CHEMISTRY; METALLURGY
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Description
Lは中性配位子であり、
X、X’は陰イオン配位子であり、
R1およびR2はそれぞれ独立して、水素、C1〜C6アルキル、C1〜C6ペルハロゲン化アルキル、アルデヒド、ケトン、エステル、アミド、ニトリル、場合により置換されるアリール、アルキルピリジニウム、ペルハロゲン化アルキルピリジニウムもしくは場合により置換されるC 5 〜C 6 シクロヘキシル、CnH2nYもしくはCnF2nY基[式中、nは1〜6からなり、Yはイオンマーカー、または次式:
化合物が式(I)である場合は、R1が式(Ibis)
あるいは化合物が式(II)である場合は、R1が式(IIbis)
R3は、C1〜C6アルキルまたはC5〜C6シクロアルキルまたはC5〜C6アリールであり、
R0、R4、R5、R6、R7、R8、R9、R10、R11はそれぞれ独立して、水素、C1〜C6アルキル、C1〜C6ペルハロゲン化アルキル、またはC5〜C6アリールであり、R9、R10、R11は複素環を形成し得、
X1は陰イオン、すなわちハロゲン、テトラフルオロホウ酸イオン([BF4]-)、[テトラキス−(3,5−ビス−(トリフルオロメチル)−フェニル)ホウ酸イオン]([BARF]-)、ヘキサフルオロリン酸イオン([PF6]-)、ヘキサフルオロアンチモン酸イオン([SbF6]-)、ヘキサフルオロ砒酸イオン([AsF6]-)、トリフルオロメチルスルホン酸イオン([CF3]2N)-)であり、
R1およびR2は、それぞれが結合するNおよびCと一緒になって、次式
の複素環を形成し得る]
のすべての化合物に関する。
n1は0、1、2、3であり、
R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R25、R26、R27、R28はそれぞれ独立して、C1〜C6アルキル、C3〜C20シクロアルキル、C2〜C20アルケニル、ナフチル、アントラセンまたはフェニルであり、前記フェニルは、C1〜C6アルキル、C1〜C6アルコキシおよびハロゲンの中から選択される最高5つの群から置換され得、R16およびR17ならびにR26およびR27は、3員、4員、5員、6員、7員の環を形成し得、R28は独立して、連結した6員の芳香族環を形成し得る]
の配位子である。
Xは塩素であり、
X’は塩素であり、
イオンマーカーYは、好ましくは
一般的な方法に従って、4−イソプロポキシ−3−ビニルアニリン5(1当量、約0.2mmol)を、窒素雰囲気にした丸底フラスコに投入し、無水ジクロロメタン(2〜3mL)に溶解した。ピリジン(1.5当量)を溶液に添加し、0℃に冷却した。次いで、塩化アシルまたは無水物(1.2当量)を緩徐に添加した後、反応媒質を窒素雰囲気下にて2時間室温で攪拌した。
一般的な方法に従って、アミド配位子(1当量)、塩化銅(I)(1当量)およびインデニリデン予備触媒(1当量)をアルゴン雰囲気下にて丸底フラスコに投入し、そこに無水ジクロロメタン(2〜3mL)を添加した。次いで、アルゴン雰囲気下にて、30〜33℃にした反応媒質から3回脱気を行い、攪拌しながら約5時間保持した。
トリフルロアセトアミド官能基を予備触媒の活性化により適した基として明確に特定されれば、イオンモチーフ(イオンタグ)の導入が可能となる。
Claims (22)
- 触媒作用のための式(I)
Lは中性配位子であり、
X、X’は陰イオン配位子であり、
R1およびR2はそれぞれ独立して、C1〜C6ペルハロゲン化アルキル、アルデヒド、ケトン、エステル、アミド、ニトリル、場合により置換されるアリール、アルキルピリジニウム、ペルハロゲン化アルキルピリジニウムもしくは場合により置換されるC5〜C6シクロヘキシル、CnH2nYもしくはCnF2nY基[式中、nは1〜6からなり、イオンマーカーYは次式:
R2は水素またはC1〜C6アルキルでもあり得、
化合物が式(I)である場合は、R1が式(Ibis)
R3は、C1〜C6アルキルまたはC5〜C6シクロアルキルまたはC5〜C6アリールであり、
R 4、R5、R6、R7、R8、R9、R10、R11はそれぞれ独立して、水素、C1〜C6アルキル、C1〜C6ペルハロゲン化アルキル、またはC5〜C6アリールであり、R9、R10、R11は複素環を形成し得、
X1は陰イオン、すなわちハロゲン、テトラフルオロホウ酸イオン([BF4]-)、[テトラキス‐(3,5‐ビス‐(トリフルオロメチル)‐フェニル)ホウ酸イオン]([BARF]-)、ヘキサフルオロリン酸イオン([PF6]-)、ヘキサフルオロアンチモン酸イオン([SbF6]-)、ヘキサフルオロ砒酸イオン([AsF6]-)、トリフルオロメチルスルホン酸イオン([CF3]2N)-)であり、
R1およびR2は、それぞれが結合するNおよびCと一緒になって、次式
の複素環を形成し得る]
の化合物。 - LがP(R13)3[式中、R13は、C1〜C6アルキルもしくはアリールまたはC5〜C6シクロアルキルである]であることを特徴とする、請求項1に記載の化合物。
- Lが、式7a、7b、7c、7dまたは7e
n1は0、1、2、3であり、
R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R25、R26、R27、R28はそれぞれ独立して、C1〜C6アルキル、C3〜C20シクロアルキル、C2〜C20アルケニル、ナフチル、アントラセンまたはフェニルであり、前記フェニルは、C1〜C6アルキル、C1〜C6アルコキシおよびハロゲンの中から選択される最高5つの群から置換され得、R16およびR17ならびにR26およびR27は、3員、4員、5員、6員、7員の環を形成し得、R28は独立して、連結した6員の芳香族環を形成し得る]
の配位子であることを特徴とする、請求項1に記載の化合物。 - LがPCy3であり、Cyがシクロヘキシルであるか、あるいはLが式7aまたは7bの配位子であり、
Xが塩素であり、
X’が塩素である
ことを特徴とする、請求項2または3に記載の化合物。 - 式(I)[式中、R1はCF3、C6F5、pNO 2 C6H4からなる群から選択される]に対応することを特徴とする、請求項4に記載の化合物。
- 式(I)[式中、R1はCF3である]に対応することを特徴とする、請求項5に記載の化合物。
- 式(III)の前記化合物が、グラブス予備触媒(2b)またはノラン予備触媒(2c)であることを特徴とする、請求項21に記載の方法。
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FR0610478A FR2909381A1 (fr) | 2006-11-30 | 2006-11-30 | Complexes de rethenium et utilisation de tels complexes pour la metathese d'olefines |
FR0700634 | 2007-01-30 | ||
FR0700634A FR2909382B1 (fr) | 2006-11-30 | 2007-01-30 | Complexes catalytiques a base de ruthenium et utilisation de tels complexes pour la metathese d'olefines |
PCT/EP2007/063062 WO2008065187A1 (fr) | 2006-11-30 | 2007-11-30 | Complexes catalytiques a base de ruthenium et utilisation de tels complexes pour la metathese d'olefines |
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WO2012013208A1 (en) | 2010-07-30 | 2012-02-02 | Ecole Nationale Superieure De Chimie De Rennes | Novel stable and highly tunable metathesis catalysts |
IN2014CN00746A (ja) | 2011-07-12 | 2015-04-03 | Basf Se | |
US8993819B2 (en) | 2011-07-12 | 2015-03-31 | Basf Se | Process for preparing cycloheptene |
WO2013010676A2 (en) | 2011-07-20 | 2013-01-24 | Ecole Nationale Superieure De Chimie De Rennes | Supported ionic liquid phase catalyst |
PL230302B1 (pl) | 2012-02-27 | 2018-10-31 | Apeiron Synthesis Spolka Z Ograniczona Odpowiedzialnoscia | Katalizatory metatezy zawierające grupy oniowe |
GB201204715D0 (en) | 2012-03-18 | 2012-05-02 | Croda Int Plc | Metathesis of olefins using ruthenium-based catalytic complexes |
JP6290195B2 (ja) | 2012-06-13 | 2018-03-07 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | 大環状ケトンの製造方法 |
AU2013283680B2 (en) | 2012-06-29 | 2016-06-16 | Apeiron Synthesis S.A. | Metal complexes, their application and methods of carrying out of metathesis reaction |
FR2992642B1 (fr) | 2012-06-29 | 2015-06-19 | Novance | Procede de synthese d’acides insatures biosources |
FR2999184B1 (fr) * | 2012-12-12 | 2015-01-09 | Ecole Nationale Superieure De Chimie De Rennes | Complexes de ruthenium comprenant un diaminocarbene n-heterocyclique insature dissymetrique |
FR3003564B1 (fr) * | 2013-03-19 | 2015-03-06 | Arkema France | Procede de metathese comprenant l'extraction de l'ethylene forme au moyen d'une membrane |
EP3008078B1 (en) | 2013-06-12 | 2018-12-19 | Trustees of Boston College | Catalysts for efficient z-selective metathesis |
GB201322936D0 (en) | 2013-12-23 | 2014-02-12 | Croda Int Plc | Polyurethane |
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CA3006976A1 (en) * | 2015-12-10 | 2017-06-15 | California Institute Of Technology | Olefin metathesis catalysts |
AR110606A1 (es) | 2016-06-06 | 2019-04-17 | Provivi Inc | Producción semi-biosintética de alcoholes grasos y aldehídos grasos |
HUE054859T2 (hu) | 2016-11-09 | 2021-10-28 | Verbio Ver Bioenergie Ag | Cserebomlási reakcióhoz alkalmazható ruténium komplexek |
FR3063290A1 (fr) | 2017-02-24 | 2018-08-31 | Stratoz | Procede de synthese de pheromones |
CN110914442A (zh) | 2017-05-17 | 2020-03-24 | 普罗维维股份有限公司 | 用于产生昆虫信息素及相关化合物的微生物 |
CN107641165B (zh) * | 2017-08-08 | 2020-05-08 | 上海克琴科技有限公司 | 钌金属催化剂DREAM-2nd及其在烯烃关环复分解和双环戊二烯聚合反应中的应用 |
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Publication number | Publication date |
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FR2909382A1 (fr) | 2008-06-06 |
EP2476688A1 (fr) | 2012-07-18 |
EP2097431B1 (fr) | 2015-03-25 |
US20100087644A1 (en) | 2010-04-08 |
BRPI0721051B1 (pt) | 2017-05-09 |
FR2909382B1 (fr) | 2009-01-23 |
US8394965B2 (en) | 2013-03-12 |
EP2097431A1 (fr) | 2009-09-09 |
CA2671082A1 (fr) | 2008-06-05 |
BRPI0721051A2 (pt) | 2014-07-29 |
CN103601758A (zh) | 2014-02-26 |
WO2008065187A1 (fr) | 2008-06-05 |
IN2009KN02409A (ja) | 2015-08-07 |
JP2010511017A (ja) | 2010-04-08 |
EP2476688B1 (fr) | 2017-06-14 |
US20130144060A1 (en) | 2013-06-06 |
CN103601758B (zh) | 2017-09-08 |
US8586757B2 (en) | 2013-11-19 |
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