EP2139853A1 - Verfahren zur herstellung von carbenvorläufern des caac-typs und ihre verwendung zur herstellung besagter carbene - Google Patents
Verfahren zur herstellung von carbenvorläufern des caac-typs und ihre verwendung zur herstellung besagter carbeneInfo
- Publication number
- EP2139853A1 EP2139853A1 EP08736019A EP08736019A EP2139853A1 EP 2139853 A1 EP2139853 A1 EP 2139853A1 EP 08736019 A EP08736019 A EP 08736019A EP 08736019 A EP08736019 A EP 08736019A EP 2139853 A1 EP2139853 A1 EP 2139853A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- formula
- represent
- aryl
- alkyl
- 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.)
- Withdrawn
Links
- 239000002243 precursor Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 79
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 60
- 125000003118 aryl group Chemical group 0.000 claims description 58
- 125000004432 carbon atom Chemical group C* 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 40
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 36
- 125000004429 atom Chemical group 0.000 claims description 31
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 31
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 29
- -1 cyclic iminium salt Chemical class 0.000 claims description 27
- 125000003545 alkoxy group Chemical group 0.000 claims description 26
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 25
- 239000002585 base Substances 0.000 claims description 25
- 125000003107 substituted aryl group Chemical group 0.000 claims description 24
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 22
- 150000002466 imines Chemical class 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 18
- 125000001424 substituent group Chemical group 0.000 claims description 18
- 150000007975 iminium salts Chemical class 0.000 claims description 17
- 125000003342 alkenyl group Chemical group 0.000 claims description 15
- 150000001450 anions Chemical class 0.000 claims description 15
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 15
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 12
- 125000000304 alkynyl group Chemical group 0.000 claims description 12
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 125000001624 naphthyl group Chemical group 0.000 claims description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 239000003444 phase transfer catalyst Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 8
- 150000004010 onium ions Chemical class 0.000 claims description 8
- 150000003141 primary amines Chemical class 0.000 claims description 8
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 7
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 7
- 125000004104 aryloxy group Chemical group 0.000 claims description 7
- 125000001072 heteroaryl group Chemical group 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000002950 monocyclic group Chemical group 0.000 claims description 6
- 125000003367 polycyclic group Chemical group 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 238000007363 ring formation reaction Methods 0.000 claims description 5
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 5
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 claims description 4
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical group OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 150000001924 cycloalkanes Chemical class 0.000 claims description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 4
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 125000002560 nitrile group Chemical group 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 3
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000005490 tosylate group Chemical group 0.000 claims description 3
- QJWHZMGVPAUALF-UHFFFAOYSA-N 2,4,6-triethylaniline Chemical compound CCC1=CC(CC)=C(N)C(CC)=C1 QJWHZMGVPAUALF-UHFFFAOYSA-N 0.000 claims description 2
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 claims description 2
- POOHDXZORPCVJE-UHFFFAOYSA-N 2,6-di(propan-2-yloxy)aniline Chemical compound CC(C)OC1=CC=CC(OC(C)C)=C1N POOHDXZORPCVJE-UHFFFAOYSA-N 0.000 claims description 2
- HQBJSEKQNRSDAZ-UHFFFAOYSA-N 2,6-dimethoxyaniline Chemical compound COC1=CC=CC(OC)=C1N HQBJSEKQNRSDAZ-UHFFFAOYSA-N 0.000 claims description 2
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 2
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 125000004450 alkenylene group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- 238000010533 azeotropic distillation Methods 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000012024 dehydrating agents Substances 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 235000010755 mineral Nutrition 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 2
- KWVPRPSXBZNOHS-UHFFFAOYSA-N 2,4,6-Trimethylaniline Chemical compound CC1=CC(C)=C(N)C(C)=C1 KWVPRPSXBZNOHS-UHFFFAOYSA-N 0.000 claims 1
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 claims 1
- 150000002430 hydrocarbons Chemical group 0.000 claims 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims 1
- DLSOILHAKCBARI-UHFFFAOYSA-N n-benzyl-2-methylpropan-2-amine Chemical group CC(C)(C)NCC1=CC=CC=C1 DLSOILHAKCBARI-UHFFFAOYSA-N 0.000 claims 1
- 239000000543 intermediate Substances 0.000 abstract description 20
- VUFNLQXQSDUXKB-DOFZRALJSA-N 2-[4-[4-[bis(2-chloroethyl)amino]phenyl]butanoyloxy]ethyl (5z,8z,11z,14z)-icosa-5,8,11,14-tetraenoate Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(=O)OCCOC(=O)CCCC1=CC=C(N(CCCl)CCCl)C=C1 VUFNLQXQSDUXKB-DOFZRALJSA-N 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 125000004122 cyclic group Chemical group 0.000 abstract description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 53
- 239000002904 solvent Substances 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000012429 reaction media Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 238000004320 controlled atmosphere Methods 0.000 description 3
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- HJHUXWBTVVFLQI-UHFFFAOYSA-N tributyl(methyl)azanium Chemical compound CCCC[N+](C)(CCCC)CCCC HJHUXWBTVVFLQI-UHFFFAOYSA-N 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- HUCQPHINKBNKRU-UHFFFAOYSA-N (4-methylphenyl)phosphane Chemical compound CC1=CC=C(P)C=C1 HUCQPHINKBNKRU-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 1
- CVIPNXAABKWPHN-UHFFFAOYSA-N 2-(1-ethenoxy-1,1,2,3,3,3-hexafluoropropan-2-yl)oxy-1,1,2,2-tetrafluoroethanesulfonyl fluoride Chemical compound C=COC(F)(F)C(F)(C(F)(F)F)OC(F)(F)C(F)(F)S(F)(=O)=O CVIPNXAABKWPHN-UHFFFAOYSA-N 0.000 description 1
- XGLVDUUYFKXKPL-UHFFFAOYSA-N 2-(2-methoxyethoxy)-n,n-bis[2-(2-methoxyethoxy)ethyl]ethanamine Chemical compound COCCOCCN(CCOCCOC)CCOCCOC XGLVDUUYFKXKPL-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 1
- IULJSGIJJZZUMF-UHFFFAOYSA-N 2-hydroxybenzenesulfonic acid Chemical compound OC1=CC=CC=C1S(O)(=O)=O IULJSGIJJZZUMF-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- GSBKRFGXEJLVMI-UHFFFAOYSA-N Nervonyl carnitine Chemical compound CCC[N+](C)(C)C GSBKRFGXEJLVMI-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 238000005937 allylation reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000005615 azonium group Chemical group 0.000 description 1
- MIAUJDCQDVWHEV-UHFFFAOYSA-N benzene-1,2-disulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1S(O)(=O)=O MIAUJDCQDVWHEV-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- SHFLYPPECXRCFO-UHFFFAOYSA-N benzyl-dimethyl-octylazanium Chemical compound CCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SHFLYPPECXRCFO-UHFFFAOYSA-N 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BEVHTMLFDWFAQF-UHFFFAOYSA-N butyl(triphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 BEVHTMLFDWFAQF-UHFFFAOYSA-N 0.000 description 1
- CIFCGXKXFRLSAF-UHFFFAOYSA-N butyl(tripropyl)azanium Chemical compound CCCC[N+](CCC)(CCC)CCC CIFCGXKXFRLSAF-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- QDYLMAYUEZBUFO-UHFFFAOYSA-N cetalkonium chloride Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 QDYLMAYUEZBUFO-UHFFFAOYSA-N 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 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
- 230000002950 deficient Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- KSRKBDUROZKZBR-UHFFFAOYSA-N diethyl-methyl-propylazanium Chemical compound CCC[N+](C)(CC)CC KSRKBDUROZKZBR-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- BYGXNRZZNBOSBD-UHFFFAOYSA-N dimethyl(diphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C)(C)C1=CC=CC=C1 BYGXNRZZNBOSBD-UHFFFAOYSA-N 0.000 description 1
- HASCQPSFPAKVEK-UHFFFAOYSA-O dimethyl(phenyl)phosphanium Chemical compound C[PH+](C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-O 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- AFAXGSQYZLGZPG-UHFFFAOYSA-N ethanedisulfonic acid Chemical compound OS(=O)(=O)CCS(O)(=O)=O AFAXGSQYZLGZPG-UHFFFAOYSA-N 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- IQLVJVXTKNBZRC-UHFFFAOYSA-N ethyl(trimethyl)phosphanium Chemical compound CC[P+](C)(C)C IQLVJVXTKNBZRC-UHFFFAOYSA-N 0.000 description 1
- GELSOTNVVKOYAW-UHFFFAOYSA-N ethyl(triphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 GELSOTNVVKOYAW-UHFFFAOYSA-N 0.000 description 1
- ATSROVAZOQKRJM-UHFFFAOYSA-N ethyl(tripropyl)phosphanium Chemical compound CCC[P+](CC)(CCC)CCC ATSROVAZOQKRJM-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000003977 halocarboxylic acids Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- PHUUEJUSWPFFOG-UHFFFAOYSA-N methyl(triphenyl)azanium Chemical compound C=1C=CC=CC=1[N+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 PHUUEJUSWPFFOG-UHFFFAOYSA-N 0.000 description 1
- AZFQCTBZOPUVOW-UHFFFAOYSA-N methyl(triphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 AZFQCTBZOPUVOW-UHFFFAOYSA-N 0.000 description 1
- PLNPRGLZZXAKGE-UHFFFAOYSA-N methyl(tripropyl)phosphanium Chemical compound CCC[P+](C)(CCC)CCC PLNPRGLZZXAKGE-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- ZUZLIXGTXQBUDC-UHFFFAOYSA-N methyltrioctylammonium Chemical compound CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC ZUZLIXGTXQBUDC-UHFFFAOYSA-N 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical compound [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L sodium sulphate Substances [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- UOBBAWATEUXIQF-UHFFFAOYSA-N tetradodecylazanium Chemical compound CCCCCCCCCCCC[N+](CCCCCCCCCCCC)(CCCCCCCCCCCC)CCCCCCCCCCCC UOBBAWATEUXIQF-UHFFFAOYSA-N 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- SZWHXXNVLACKBV-UHFFFAOYSA-N tetraethylphosphanium Chemical compound CC[P+](CC)(CC)CC SZWHXXNVLACKBV-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- OKBQUWUVZGPEQZ-UHFFFAOYSA-N tributyl(hexadecyl)phosphanium Chemical compound CCCCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC OKBQUWUVZGPEQZ-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- TZWFFXFQARPFJN-UHFFFAOYSA-N triethyl(methyl)phosphanium Chemical compound CC[P+](C)(CC)CC TZWFFXFQARPFJN-UHFFFAOYSA-N 0.000 description 1
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 description 1
- MYKCGIGJOAYNOG-UHFFFAOYSA-N trimethyl(pentyl)phosphanium Chemical compound CCCCC[P+](C)(C)C MYKCGIGJOAYNOG-UHFFFAOYSA-N 0.000 description 1
- WHAFDJWJDDPMDO-UHFFFAOYSA-N trimethyl(phenyl)phosphanium Chemical compound C[P+](C)(C)C1=CC=CC=C1 WHAFDJWJDDPMDO-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/54—Spiro-condensed
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/06—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with radicals, containing only hydrogen and carbon atoms, attached to ring carbon atoms
Definitions
- the subject of the present invention is a process for the preparation of carbene precursors of the CAAC (Cyclic) (Alkyl) (Amino) (Carbenes) type and their use for preparing said carbenes.
- the invention relates to the use of novel synthetic intermediates for preparing carbene precursors of CAAC type.
- the carbenes are compounds that can be used as organocatalysts or as metal ligands such as palladium, platinum, nickel, ruthenium, rhodium, iridium, copper and iron thus forming stable organometallic complexes which can be used as catalysts for organic reactions, especially in the coupling reactions between an electrophilic reagent, most often an aromatic compound carrying a leaving group (such as halogen, sulphonic ester, azonium, etc.) and a nucleophilic compound providing a a carbon atom or a heteroatom capable of substituting for the leaving group, thus creating a CC or C-HE bond (HE being a heteroatom for example N 1 O, S, Si ).
- a leaving group such as halogen, sulphonic ester, azonium, etc.
- CAACs alkylaminocyclic carbene
- Cyclic (Alkyl) (Amino) Carbenes are known compounds and described in the literature in particular in WO 2006/138166.
- a synthesis route of said carbene is represented by the following reaction scheme: TfOTf
- the Applicant proposes a method to avoid this disadvantage by involving a different intermediate product.
- the subject of the present invention is the use, as intermediate for the production of a CAAC carbene precursor, of a compound corresponding to the following formula:
- w is equal to 1 or 2
- R 1, R 2 which may be identical or different, represent an alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, alkoxy, alkenyloxy, alkynyloxy, aryloxy or alkoxycarbonyl group,
- R 1 and R 2 can be bonded together to form a spirocycle comprising from 3 to 18 atoms
- R'1, R ' 2 , R'3, R'4, R'5, identical or different, represent a hydrogen atom, an alkyl group, cycloalkyl, aryl, aralkyl.
- alkyl is understood to mean a linear or branched hydrocarbon chain containing from 1 to 15 carbon atoms, preferably from more preferably in CrC 4 .
- alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl and t-butyl.
- alkoxy is meant an alkyl-O- group in which the term alkyl has the meaning given above.
- Preferred examples of alkoxy groups are methoxy or ethoxy.
- alkoxycarbonyl is meant the alkoxy-C (O) - group in which the alkoxy group has the definition given above.
- alkenyl means a straight or branched hydrocarbon chain having one double bond, C2-C8, preferably C2-C6 and most preferably C2-C4.
- alkenyl groups include vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl and isobutenyl.
- alkynyl is meant a linear or branched hydrocarbon chain comprising a C 2 -C 8 , preferably C 2 -C 6 and even more preferentially C 2 -C 4, triple bond.
- alkynyl groups include ethynyl, 1-propynyl, 1-butynyl, 2-butynyl.
- alkenyloxy and alkynyloxy are meant respectively an alkenyl-O- and alkynyl-O- group in which the terms alkenyl and alkynyl have the meanings given above.
- cycloalkyl is meant a cyclic hydrocarbon group, monocyclic C3-C10 preferably a cyclopentyl or cyclohexyl or polycyclic (bicyclic or tricyclic) C 4 -C 8 , in particular adamantyl or norbornyl.
- cycloalkane spirocycle is meant as previously defined, a mono- or polycyclic structure, C 8 -C 18, preferably C 3 -C 3
- aryl is meant an aromatic mono- or polycyclic group, preferably mono- or bicyclic C 6 -C 20 , preferably phenyl or naphthyl.
- the group is polycyclic, that is to say that it comprises more than one ring nucleus, the ring nuclei can be condensed two by two or attached in pairs by bonds ⁇ .
- groups (C 6 -C 8) aryl include phenyl, naphthyl.
- aryloxy is meant an aryl-O- group in which the aryl group has the meaning given above.
- arylalkyl is meant a hydrocarbon group, linear or branched bearer of a monocyclic aromatic ring C 7 -C 2, preferably benzyl: the aliphatic chain contains 1 or 2 carbon atoms It should be noted that since one of the groups R 1, R 2, R '1, R' 2, R '3, R' 4, R '5 comprises a ring, this ring may be substituted by one or more preferably two or three substituents. The nature of the substituent can be any since it does not interfere at the level of the CAAC synthesis.
- substituents represented by R 1 include alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, amino, amino groups substituted by alkyl, cycloalkyl groups; a nitrile group; a halogen atom, preferably chlorine or fluorine; a haloalkyl group, preferably perfluoromethyl.
- the compounds of formula (I) are referred to as "intermediate compounds" because they are intermediates for the production of carbene precursors.
- the preferred intermediate compounds have the formula (Ia) or (Ib):
- R 1, R 2 which may be identical or different, represent an alkyl group, an optionally substituted aryl group, preferably an optionally substituted phenyl or naphthyl group,
- R 1 and R 2 are bonded together to form a spirocyclic ring of cycloalkane, mono- or polycyclic type
- R ' 3 , R 4 , R' 5 which may be identical or different, represent an alkyl group
- R 4 , R ' 5 also represent a hydrogen atom.
- R 1, R 2 represent an optionally substituted aryl group;
- the substituent (s) may be as previously defined (R t ) but are preferably alkyl groups and / or alkoxy groups and / or aryl groups, preferably phenyl.
- the intermediate compounds prepared more preferably correspond to formula (Ia) or (Ib) in which:
- R 1, R 2 which may be identical or different, represent a linear or branched alkyl group having from 1 to 4 carbon atoms or a phenyl group, a substituted phenyl group,
- R 1 and R 2 are linked together to form a cyclopentane, a cyclohexane or a norbornane,
- R'3, R ' 4 , R' 5 identical or different, represent a linear or branched alkyl group having 1 to 4 carbon atoms and R ' 4 , R' 5 also represent a hydrogen atom.
- Another subject of the invention lies in the process for the preparation of a carbene precursor CAAC, also called "iminium salt" of formula
- R represents an alkyl, cycloalkyl, aryl, aralkyl or heteroaryl group
- R 1, R 2 which may be identical or different, represent an alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, alkoxy, alkenyloxy, alkynyloxy, aryloxy or alkoxycarbonyl group,
- R 1 and R 2 can be bonded together to form a spirocycle comprising from 3 to 18 atoms
- A represents a ring comprising 5 or 6 atoms of which at least one of the atoms is a nitrogen atom as represented,
- L is a divalent group corresponding to the following formula:
- w is a number equal to 1 or 2
- R'1, R ' 2 , R'3, R'4, R'5, identical or different, represent a hydrogen atom, an alkyl group, cycloalkyl, aryl, aralkyl,
- Z is an anion, characterized in that it comprises at least one reaction step of: - the compound of formula (I):
- R1, R2, R'1, R'2, R'3, R'4, R'5 and w have the meaning given above,
- R represents an alkyl, cycloalkyl, aryl, aralkyl or heteroaryl group
- R, R 1, R 2 , R ' 1 , R' 2 , R 's, R' 4 , R 's and w have the meaning given above.
- the intermediate compound of formula (I) is prepared by reaction of an aldehyde having at least one hydrogen atom in position ⁇ with respect to the carbonyl group and an unsaturated reagent, a leaving group, in bi-phasic medium, in the presence of a strong base and a phase transfer catalyst.
- Another object of the invention resides in the process for preparing a CAAC carbene precursor of formula (VI) according to a cyclization step of the compound of formula (IV).
- the preparation of the intermediate compound of formula (I) is carried out according to a preparation process which comprises the reaction of an aldehyde having at least one hydrogen atom in position ⁇ with respect to the carbonyl group and an unsaturated reagent bearing a leaving group in a bi-phasic medium in the presence of a strong base and a phase transfer catalyst.
- R 1, R 2 which may be identical or different, represent an alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, alkoxy, alkenyloxy, alkynyloxy, aryloxy or alkoxycarbonyl group,
- R 1 and R 2 may be bonded together to form a spirocycle comprising from 3 to 18 atoms, and an unsaturated reagent carrying a leaving group:
- - w is a number equal to 1 or 2
- R ', R'2, R'3, R 4, R' 5, identical or different, represent a hydrogen atom, alkyl, cycloalkyl, aryl, aralkyl,
- Y represents a leaving group
- Y represents a leaving group selected from bromine, chlorine or a sulphonic ester group of formula - OSO 2 - R e , in which R e is a hydrocarbon group.
- R e is a hydrocarbon group of any kind.
- Y is a leaving group, it is interesting from an economic point of view that R e is of a simple nature, and more particularly represents a linear or branched alkyl group having from 1 to 4 carbon atoms, preferably, a methyl or ethyl group but it may also represent for example a phenyl or tolyl group or a trifluoromethyl group.
- the preferred group is a triflate group which corresponds to a group R e representing a trifluoromethyl group.
- a chlorine atom is preferably selected.
- the amount of unsaturated reagent of formula (III) to be used expressed relative to the amount of the aldehyde of formula (II) is at least equal to the stoichiometry.
- the ratio between the number of unsaturated reactive moles of formula (III) and the number of moles of aldehyde of formula (II) varies between 1 and 1.5, and is preferably between 1, 2 and 1.3. .
- a base which can be inorganic or organic.
- the base used must be strong enough to allow the anionization of the carbon - hydrogen bond of the aldehyde.
- strong base is meant a base whose pka of the conjugated acid is greater than or equal to 9, preferably between 10 and 14.
- PKa is defined as the ionic dissociation constant of the acid / base pair, when water is used as the solvent.
- a base having a pKa as defined by the invention reference may be made, inter alia, to the HANDBOOK OF CHEMISTRY AND PHYSICS, 66 th edition, p. D-161 AND D-162.
- a mineral base such as an alkali or alkaline earth metal hydroxide, preferably sodium hydroxide, potassium hydroxide or lithium hydroxide; an alkali metal phosphate or hydrogenphosphate, preferably sodium or potassium phosphate or an organic base, preferably sodium methoxide.
- quaternary ammonium hydroxide preference is given to the use of tetraalkylammonium or trialkylbenzylammonium hydroxides, the identical or different alkyl groups of which represent a linear or branched alkyl chain having from 1 to 12 carbon atoms, from preferably 1 to 6 carbon atoms.
- Tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide or trimethylbenzylammonium hydroxide are preferably chosen.
- the base is used, indifferently in the form of a powder or in the form of an aqueous solution.
- the concentration of the basic starting solution is not critical.
- the alkali metal hydroxide solution used has a concentration generally of between 10 and 50% by weight.
- the amount of base used expressed by the ratio between the number of moles of OH ' ions and the number of moles of compound of formula (II) varies between 2 and 5, preferably between 3 and 4.
- reaction of the compounds of formulas (II) and (III) is conducted in the absence or in the presence of an organic solvent.
- the organic solvent is chosen such that it is inert under the reaction conditions of the invention.
- aromatic hydrocarbons such as toluene, xylenes, cumene, mesitylene, petroleum fractions consisting of a mixture of alkylbenzenes, in particular Solvesso type cuts, and decalin.
- the amount of solvent used is determined in such a way that the concentration of the compound of formula (II) in the organic solvent is preferably between 2 and 10 mol / liter, preferably around 3 mol / liter.
- phase transfer catalyst a catalyst capable of passing the anion from the aqueous phase to the organic phase.
- phase transfer catalysts in particular, those described in the book by Jerry March - Advanced Organic Chemistry, 4th Edition, John Wiley & Sons, 1992 p. 362 and following.
- the onium salts that can be used in the process of the invention are those whose onium ions derive in particular from nitrogen, phosphorus, sulfur, oxygen, carbon or iodine and coordinated to hydrocarbon residues.
- hydrocarbon residues coordinated to these various elements are optionally substituted alkyl, alkenyl, aryl, cycloalkyl or aralkyl groups, two coordinated hydrocarbon radicals which can together form a single divalent group.
- onium ions which can be used in the present process of the invention, those having the following general formula are particularly suitable: X 1 ⁇ / X 2
- Z 1 represents N or P
- X 1 , X 2 , X 3 , X 4 which are identical or different, represent: an alkyl group, linear or branched, having 1 to 16 carbon atoms and optionally substituted by one or more groups or atoms phenyl, hydroxyl, halogen, nitro, alkoxy or alkoxycarbonyl, alkoxy groups having 1 to 4 carbon atoms,. a linear or branched alkenyl group having 2 to 12 carbon atoms,
- an aryl group having 6 to 10 carbon atoms optionally substituted by one or more alkyl groups or atoms having 1 to 4 carbon atoms, alkoxy, alkoxycarbonyl, the alkoxy group having 1 to 4 carbon atoms, or halogen,
- two of said groups X 1 to X 4 may together form a linear or branched alkylene, alkenylene or alkadienylene group having from 3 to 6 carbon atoms.
- said anions may be chosen from PO 4 3 -, HPO 4 2 “ , H 2 PO 4 “ , CH 3 SO 3 “ , Ph-SO 3 “ , NO 3 “ , SO 4 2 “ , PF 6 “ , CI “ , Br “ , I “ , Ph having the above meaning.
- the quaternary ammonium ions the quaternary phosphonium ions, will most often be preferred.
- Ammonium or phosphonium ions whose four groups are alkyl groups having from 1 to 5 carbon atoms or a benzyl group are particularly particularly suitable.
- the anion Br “ , CI “ , OH “ , HSO 4 " will be preferred.
- Catalysts very well suited to the present invention are thbutylbenzylammonium or phosphonium chloride or bromide, tetramethylammonium or phosphonium chloride or bromide, chloride or tetraethylammonium bromide or phosphonium bromide, tetrabutylammonium chloride or bromide or phosphonium.
- Benzyltributlylammonium chloride or bromide is particularly preferred, the chlorinated derivative being more particularly preferred.
- the onium salt may be introduced during the process of the invention, in the solid state or in the form of a solution in one of its solvents, most often water.
- phase transfer catalysts that may be used in the process of the invention include tri (ether-amines), especially those described in FR-A-2,455,570, which have the following formula:
- R 3 represents an alkyl group having 1 to 24 carbon atoms, a cyclohexyl group, a phenyl group, an alkylphenyl group containing from 7 to 12 carbon atoms,
- a and B which are identical or different, represent a linear alkanediyl group containing 2 or 3 carbon atoms optionally substituted by a methyl or ethyl group, n is an integer between 0 and 4.
- catalysts of formula (F 2 ) there may be mentioned ths (dioxa-3,6-heptyl) amine sold under the name TDA-1.
- a preferred embodiment comprises the parallel introduction of the compounds of formula (II) and (III) in a medium comprising the solvent (water and / or organic solvent), the base and the phase transfer catalyst.
- the introduction of the compounds of formulas (II) and (III) is advantageously carried out progressively, fractionally or continuously.
- the duration of addition is for example between 2 and 10 hours, preferably between 4 and 5 hours.
- the coupling reaction between the compounds of formula (II) and (III) is generally carried out at a temperature ranging between 50 ° C. and 100 ° C., preferably between 70 ° and 80 ° C.
- the process of the invention is carried out under atmospheric pressure but preferably under a controlled atmosphere of inert gases such as nitrogen or rare gases, for example argon. A pressure slightly above or below atmospheric pressure may be suitable.
- R1, R2, R'1, R'2, R'3, R'4, R'5 and w have the meaning given above.
- the said compound is recovered from the reaction medium which comprises an organic phase comprising the addition product of formula (I) and the reagents (II) or (III) in excess and an aqueous phase comprising the salts resulting from the reaction.
- the organic and aqueous phases are separated.
- the aqueous phase can be washed once or twice with the aid of an organic solvent, preferably the solvent chosen for the reaction.
- the organic phases are combined and then a usual drying operation is preferably carried out on desiccant, for example sodium or magnesium sulphate.
- desiccant for example sodium or magnesium sulphate.
- the reaction medium is generally concentrated by evaporation and then the intermediate compound of formula (I) is recovered in a conventional manner, preferably by distillation.
- R1, R2, R'1, R'2, R'3, R'4, R'5 and w have the meaning given above,
- R represents an alkyl, cycloalkyl, aryl, aralkyl or heteroaryl group, characterized in that it is obtained by reaction in the presence of a strong acid, of the compound of formula (I) with a primary amine of formula (V) :
- R represents an alkyl, cycloalkyl, aryl, aralkyl or heteroaryl group.
- heteroaryl is meant an aryl group as defined above, one to three carbon atoms may be replaced by a heteroatom, preferably oxygen or nitrogen.
- the group R is a preferred hydrocarbon group which is sterically hindered.
- the substituents on the phenyl group are preferably in the ortho and / or para and / or ortho position relative to the amino group.
- the substituents on the naphthyl group are preferably in the ortho and / or ortho position relative to the amino group.
- reaction of the compound of formula (I) and of the primary amine of formula (V) can be carried out according to a basic catalysis that is to say without catalyst when the amine is sufficiently basic, that is to say that his pka in the water is greater than or equal to 10.
- reaction of the compound of formula (I) and the primary amine of formula (V) may also be catalyzed by an acid.
- the reaction is carried out in the presence of a catalytic amount of a strong protonic acid, that is to say an acid having a pKa in water of less than 5, preferably less than 1.
- strong protic acids include, inter alia, sulfuric acid, chlorosulfuric acid, perchloric acid; sulphonic acids such as, for example, methanesulphonic acid, trifluoromethanesulphonic acid, toluenesulphonic acid, phenolsulphonic acid; carboxylic acids such as acetic acid, trifluoroacetic acid.
- protic acid catalysts include sulfonic resins and more particularly resins marketed under different commercial names.
- the following resins can be mentioned, among others: TEMEX 50, AMBERLYST 15, AMBERLYST 35, AMBERLYST 36,
- the above resins consist of a polystyrene backbone which carries functional groups which are sulfonic groups.
- the polystyrene backbone is obtained by polymerization of styrene and divinylbenzene, under the influence of an activation catalyst, most often an organic peroxide, which leads to a cross-linked polystyrene which is then treated with sulfuric acid or concentrated sulphochloride resulting in a sulfonated styrene-divinylbenzene copolymer.
- sulphonic resins which are phenol-formaldehyde copolymers and which relate to the aromatic ring a methylenesulphonic group, for example the resin marketed under the name DUOLITE ARC 9359.
- resins available on the market are also suitable and mention may be made of perfluorinated resins bearing sulphonic groups and, more particularly, NAFION, which is a copolymer of tetrafluoroethylene and of perfluoro [2- (fluorosulfonylethoxy) propyl] vinyl ether.
- NAFION is a copolymer of tetrafluoroethylene and of perfluoro [2- (fluorosulfonylethoxy) propyl] vinyl ether.
- methanesulfonic acid or p-toluenesulfonic acid is preferably used.
- the amount of acid used is preferably catalytic.
- the amount of acid expressed relative to the amount of aldehyde represents from 1 to 10% by weight, preferably from 1 to 5% by weight of aldehyde when the latter is defective in relation to the amine of formula (V).
- the reaction is conducted in the presence of an organic solvent or not.
- organic solvents examples include, in particular, aliphatic, cycloaliphatic, aromatic, halogenated or non-halogenated hydrocarbons, and more particularly hexane, heptane, isooctane, decane, benzene and toluene. , methylene chloride, chloroform.
- the amount of solvent used is such that the concentration of the compound of formula (I) varies between 5 and 50% by weight of the reaction mixture.
- the strong acid is brought into the presence of the mixture of the compound of formula (I) and the amine of formula (V) in the organic solvent.
- the reaction mixture is subjected to azeotropic distillation.
- the distillation is carried out at a temperature of between 40 ° C. and 120 ° C., at atmospheric pressure or under reduced pressure ranging from 10 mm of mercury to atmospheric pressure, preferably of between 10 and 200 mm. mercury.
- R, R 1, R 2, R '1, R' 2, R '3, R' 4, R '5 and w have the meaning given above.
- the imine is recovered by evaporation of the solvent, in particular by distillation under reduced pressure, for example between 1 and 100 mm of mercury.
- Another alternative embodiment of the invention consists in eliminating the water formed in the reaction with the aid of a dehydrating agent, for example magnesium sulphate or a 4A aluminosilicate molecular sieve.
- a dehydrating agent for example magnesium sulphate or a 4A aluminosilicate molecular sieve.
- the invention also relates to the use of the imine compound of formula (IV) for the preparation of a cyclic iminium salt having the general formula (VI):
- A represents a ring comprising 5 or 6 atoms of which at least one of the atoms is a nitrogen atom as represented,
- L is a divalent group corresponding to the following formula:
- w is a number equal to 1 or 2
- R ' 2 , R'3, R'4, R'5, identical or different, represent a hydrogen atom, an alkyl group, cycloalkyl, aryl, aralkyl,
- R, R 1, R 2 have the meaning given above
- Z represents an anion such as, for example, a halide, preferably a chloride (in the form of CI “ , HCl 2 " or a mixture thereof) or a bromide, an acetate, trifluoroacetate, mesylate or tosylate group.
- a halide preferably a chloride (in the form of CI " , HCl 2 " or a mixture thereof) or a bromide, an acetate, trifluoroacetate, mesylate or tosylate group.
- the compound of formula (VI) is prepared from the linear iminium salt obtained by reaction of the compound of formula (IV) and a strong acid and then cyclization of the linear iminium salt obtained.
- a strong acid is used.
- strong protonic acids there may be mentioned more particularly hydracids such as hydrochloric acid, hydrobromic acid; halogenated or non-halogenated oxyacids such as sulfuric acid, perchloric acid; halogenated or unsaturated sulphonic acids such as fluorosulphonic acid, chlorosulphonic acid or trifluoromethanesulphonic acid, methanesulphonic acid, ethanesulphonic acid, ethanedisulphonic acid, benzenesulphonic acid, benzenedisulphonic acids, toluenesulphonic acids xylenesulphonic acids, naphthalenesulphonic acids and naphthalenesulphonic acids; halocarboxylic acids such as in particular trichloroacetic acid.
- hydrochloric acid is preferably used.
- Concentrated solutions of acid are preferably used because the presence of water in the medium slows the reaction kinetics.
- a solution of hydrochloric acid at 37% by weight at a sulfuric acid solution of at least 95%, preferably greater than 98%.
- hydrochloric acid is used in gaseous form.
- the amount of acid expressed as the ratio of the number of proton equivalents to the number of moles of compound of formula (IV) may vary from about 1 to about 10, and preferably from 2 to 3.
- the process of the invention is generally carried out under atmospheric pressure, but preferably under a controlled atmosphere of inert gases. It is possible to establish an atmosphere of rare gases, preferably argon, but it is more economical to use nitrogen.
- the compound of formula (IV) and an organic solvent are charged, and then the acid is introduced, preferably bubbling with hydrochloric acid.
- the temperature of the reaction is advantageously between about
- the addition of the acid is in a progressive manner, continuously or in fractions for a period preferably varying between 3 and 8 hours.
- reaction medium is brought to a reaction temperature preferably chosen between 60 ° C. and 100 ° C., and more preferably between 70 ° C. and 90 ° C.
- R, R 1, R 2, Z, A and L have the meaning given above.
- Z is preferably a chloride (as CI “ , HCI 2 " or a mixture thereof).
- the carbene is generated from the cyclic iminium salt of formula (VI) by reacting the latter with a strong base.
- butyllithium sodium tert-butylate or potassium
- sodium amide sodium hydride
- the strong base may be in liquid or solid form, preferably in solid form.
- the amount of base expressed relative to the cyclic iminium salt of formula (VI) generally varies from the stoichiometric amount up to an excess of up to 200%.
- the reaction is carried out at low temperature between -78 ° C and 25 ° C.
- the reaction is conducted generally under atmospheric pressure but preferably under a controlled atmosphere of inert gases. It is possible to establish an atmosphere of rare gases, preferably argon, but it is more economical to use nitrogen.
- the reaction is conducted under anhydrous conditions and in an aprotic organic solvent which is polar or non polar, selected inert under the conditions of the reaction.
- the organic solvent contain less than 5 ppm water.
- organic solvents mention may be made, inter alia, of aliphatic, cycloaliphatic or aromatic hydrocarbons and more particularly hexane, heptane, isooctane, decane, benzene, toluene; ether type solvents and especially diethyl ether, tetrahydrofuran, methyltetrahydrofuran.
- the amount of organic solvent used is such that the concentration of the cyclic iminium salt of formula (VI) varies between 10 and 50% of the weight of the reaction medium.
- the base is introduced into the organic solvent comprising the cyclic iminium salt of formula (VI).
- the carbene is recovered in a conventional manner from the reaction medium.
- the salts formed precipitate and are separated for example by filtration.
- the solvent is more polar, such as THF, it is possible to precipitate the salts formed by adding a non-polar solvent such as toluene.
- the carbene is found in the organic solvent and is recovered after evaporation of the solvent.
- the process of the invention thus makes it possible to prepare carbenes of the type
- CAACs that can be represented by the following formula:
- - R, R 1, R 2 have the meaning given above, - A represents a ring comprising 5 or 6 atoms, at least one of the atoms is a nitrogen atom as shown,
- L is a divalent group corresponding to the following formula:
- R'1, R'2, R'3, R ' 4 , R'5 and w have the meaning given above, - (x) and (y) respectively locate the two bonds established between the carbon atom bearing groups R 1 and R 2 and the nitrogen atom carrying the group R.
- CAAC carbenes prepared preferentially according to the process of the invention correspond to the formula (VII) in which A represents a ring of 5 or 6 atoms and L represents a divalent group comprising 2 or 3 atoms.
- R, R 1, R 2 have the meaning given for formula (I),
- R ' 3 , R 4 , R'5, identical or different, represent a hydrogen atom, an alkyl group, cycloalkyl, aryl, aralkyl.
- Even more preferred carbenes have the formula (VIIa) or (VIIb) wherein R is an alkyl group, an optionally substituted aryl group, preferably an optionally substituted phenyl group; R 1, R 2 , which may be identical or different, represent an alkyl group, an optionally substituted aryl group, preferably an optionally substituted phenyl group or R 1 and R 2 are linked together to form a cycloalkane; R'3, R 4 , R ' 5, which may be identical or different, represent an alkyl group and R 4 and R' 5 also represent a hydrogen atom.
- the process of the invention is quite suitable for preparing CAAC carbenes which have the formula (VIIa) or (VIIb) in which: - R represents a tert-butyl group, a phenyl group, a phenyl group substituted by a with three alkyl groups having from 1 to 4 carbon atoms,
- R 1, R 2 which may be identical or different, represent a linear or branched alkyl group having from 1 to 4 carbon atoms or a phenyl group, or R 1 and R 2 are linked together to form a cyclopentane, a cyclohexane or a norbornane,
- R'3, R ' 4 , R' 5 identical or different, represent a linear or branched alkyl group having 1 to 4 carbon atoms and R ' 4 , R' 5 also represent a hydrogen atom.
- R' 4 , R' 5 also represent a hydrogen atom. Examples of preferred carbenes are given below:
- Another object of the invention is, as new products, intermediates, imines precursors of iminium salt corresponding to the following formula:
- R represents a branched alkyl group, an aryl group, a substituted aryl group,
- R 1, R 2 which may be identical or different, represent an optionally substituted alkyl or aryl group
- R 1 and R 2 can be bonded together to form a spirocycle comprising from 3 to 18 atoms
- - R ' 3 represent a hydrogen atom, an alkyl group, an aryl group, a substituted aryl group, - R 4 , R' 5 , which may be identical or different, represent a hydrogen atom, an alkyl group or an aryl group; a substituted aryl group.
- the aryl group is a phenyl or naphthyl group and the substituted aryl group is a phenyl or naphthyl group substituted by one or more alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, amino, amino groups. substituted with alkyl, cycloalkyl groups; a nitrile group; a halogen atom, preferably chlorine or fluorine; a haloalkyl group, preferably perfluoromethyl.
- R represents a tert-butyl group; a phenyl group substituted with 3 methyl or ethyl groups in o, o 'and p positions; a phenyl group substituted with 2 isopropyl or tert-butyl groups in o and o 'position; a phenyl group substituted with 3 isopropyl or tert-butyl groups at o, o 'and p, R 1, R 2, which are identical or different, represent a methyl, ethyl, propyl, isopropyl, phenyl or substituted phenyl group;
- R 1 and R 2 may be bonded together to form a spirocycle comprising from 3 to 10 atoms, R '3 represents a methyl group,
- R 4 , R ' 5 identical or different, represent a hydrogen atom, a methyl group.
- the preferred imines according to the invention correspond to the formula (IVa), in which at least one of the groups R 1, R 2 represent an optionally substituted aryl group, preferably an optionally substituted phenyl group.
- the group R represents an optionally substituted aryl group, preferably an optionally substituted phenyl group.
- the invention relates more particularly to imines corresponding to formula (IVa) in which: - R represents a phenyl group substituted by 2 isopropyl groups in the o and o 'position; a phenyl group substituted with 3 methyl or isopropyl groups at o, o 'and p,
- R 1, R 2 identical or different, represent a methyl group, a phenyl group, a substituted phenyl group, or R 1 and R 2 may be bonded together to form a spirocycle comprising from 3 to 10 atoms,
- R 4 , R ' 5 represent a hydrogen atom.
- R s which are identical or different, represent a substituent chosen from alkyl or alkoxy groups having from 1 to 4 carbon atoms, m is the number of substituents equal to 1, 2 or 3, preferably 2 or 3,
- R 1 represent one or more substituents having the meaning given above
- R 4 , R ' 5 represent a hydrogen atom.
- the invention also aims, as new products, the iminium salts, precursors of carbenes, corresponding to the following formula:
- Z represents an anion preferably, a halide, chloride (in the form CI " , HCl 2 " or their mixture) or bromide; an acetate group; a trifluoroacetate group; a mesylate group; a tosylate group,
- R represents a branched alkyl group, an aryl group, a substituted aryl group,
- R 1, R 2 identical or different, represent an alkyl group, an aryl group, a substituted aryl group,
- R 1 and R 2 may be bonded together to form a spirocycle comprising from 3 to 18 atoms, - R ' 3 represent a hydrogen atom, an alkyl group, an aryl group, a substituted aryl group,
- R 4 , R ' 5 identical or different, represent a hydrogen atom, an alkyl group, an aryl group, a substituted aryl group, with the exception of R 1 and R 2 can not be simultaneously two methyl groups or form a cyclohexane when R is a 1,3-diisopropylphenyl group, and R 1 and R 2 can not be methyl and phenyl or form cyclohexane when R is tert-butyl.
- the preferred iminium salts correspond to the formula (VIa) in which:
- R represents a tert-butyl group; a phenyl group substituted with 3 methyl or ethyl groups in o, o 'and p positions; a phenyl group substituted with 2 isopropyl or tert-butyl groups in o and o 'position; a phenyl group substituted with 3 isopropyl or tert-butyl groups at o, o 'and p, R 1, R 2, which are identical or different, represent a methyl, ethyl, propyl, isopropyl, phenyl or substituted phenyl group;
- R 1 and R 2 may be bonded together to form a spirocycle comprising from 3 to 10 atoms, R '3 represent a hydrogen atom, a methyl group,
- R 4 , R ' 5 identical or different, represent a hydrogen atom, a methyl group.
- the invention relates to the iminium salts corresponding to the formula (VIa) in which: R represents a phenyl group substituted with 2 isopropyl groups at the o and o 'position; a phenyl group substituted with 3 methyl or isopropyl groups at o, o 'and p,
- R 1, R 2 identical or different, represent a methyl group, a phenyl group, a substituted phenyl group, or R 1 and R 2 may be bonded together to form a spirocycle comprising from 3 to 10 atoms,
- R 4 , R ' 5 represent a hydrogen atom.
- the preferred iminium salts which include two aryl groups, are schematized by the formula (Vlai).
- the groups R s which are identical or different, represent a substituent chosen from alkyl or alkoxy groups having from 1 to 4 carbon atoms,
- n is the number of substituents equal to 1, 2 or 3, preferably 2 or 3,
- - R t represent one or more substituents having the meaning given above, - R 4 , R ' 5 , represent a hydrogen atom.
- Z is preferably a chloride (in the form CI “ , HCI2 " or their mixture).
- the yield given in the examples corresponds to the ratio between the number of moles of product formed and the number of moles of substrate involved.
- an unsaturated reagent which is an allyl halide (1.3 equivalents) and an aldehyde ⁇ - disubstituted (1 equivalent) to which is added dropwise, a mixture of an aqueous solution containing 50% by weight of sodium hydroxide, an organic solvent and tetrabutylammonium bromide (4% molar) at 70-80 0 C (m.p. 'oil).
- the organic solvent is toluene in all the examples with the exception of Examples 2 and 3 where it is 2-isopropylbenzene.
- the mixture is stirred for 4.5 h at 70-80 0 C, cooled to room temperature and then extracted with distilled water.
- the aqueous phase is extracted with the solvent used then the organic phase is dried over MgSO 4 and filtered on No. 4 sintered glass.
- the solvent of the filtrate is evaporated under reduced pressure of approximately 50 mm of mercury (Rotavapor) and the filtrate is distilled under reduced pressure.
- the toluene is then evaporated under reduced pressure of approximately 50 mm of mercury (Rotavapor), then the pellet is distilled under reduced pressure.
- the medium is then filtered, the filtrate evaporated under reduced pressure of approximately 50 mm Hg (Rotavapor) and then distilled under reduced pressure.
- the imine is dissolved in toluene (solvent) and the solution is cooled to 0 ° C. A bubbling of HCl gas is maintained in the solution at 0 ° C. for 5 hours.
- reaction medium is heated at 80 ° C. for 12 hours: a white precipitate is observed (glass wool).
- Sintered glass filtration No. 4 and washing with ether makes it possible to recover a fine white powder which corresponds to the cyclized product.
- the yield obtained is 80%.
- the imine is dissolved in toluene and the solution is cooled to 0 ° C.
- a bubbling of HCl gas is maintained in the solution at 0 0 C for 5 hours.
- the imine is dissolved in toluene and the solution is cooled to 0 ° C.
- This white powder corresponds to the cyclized product.
- the temperature is lowered to -78 ° C. and 25 ml of dry THF are added.
- the THF is evaporated under a reduced pressure of 10 mm Hg.
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Application Number | Priority Date | Filing Date | Title |
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FR0702665A FR2914921A1 (fr) | 2007-04-12 | 2007-04-12 | Procede de preparation de precurseurs de carbenes de type caac et leur utilisation pour preparer lesdits carbenes |
PCT/EP2008/054295 WO2008125568A1 (fr) | 2007-04-12 | 2008-04-09 | Procede de preparation de precurseurs de carbenes de type caac et leur utilisation pour preparer lesdits carbenes |
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EP2139853A1 true EP2139853A1 (de) | 2010-01-06 |
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EP08736019A Withdrawn EP2139853A1 (de) | 2007-04-12 | 2008-04-09 | Verfahren zur herstellung von carbenvorläufern des caac-typs und ihre verwendung zur herstellung besagter carbene |
Country Status (4)
Country | Link |
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US (1) | US20100113791A1 (de) |
EP (1) | EP2139853A1 (de) |
FR (1) | FR2914921A1 (de) |
WO (1) | WO2008125568A1 (de) |
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US7678749B2 (en) * | 2007-12-17 | 2010-03-16 | International Flavors & Fragrances Inc. | Organoleptic compounds |
US8237003B2 (en) | 2009-11-09 | 2012-08-07 | Exxonmobil Chemical Patents Inc. | Metathesis catalyst and process for use thereof |
US8809563B2 (en) | 2009-11-09 | 2014-08-19 | Exxonmobil Chemical Patents Inc. | Metathesis catalyst and process for use thereof |
US8329921B2 (en) | 2009-11-09 | 2012-12-11 | Exxonmobil Chemical Patents Inc. | Metathesis catalyst and process for use thereof |
US9024034B2 (en) | 2009-11-09 | 2015-05-05 | Exxonmobil Chemical Patents Inc. | Metathesis catalysts and processes for use thereof |
US8227371B2 (en) | 2010-09-24 | 2012-07-24 | Exxonmobil Chemical Patents Inc. | Class of olefin metathesis catalysts, methods of preparation, and processes for the use thereof |
US9181360B2 (en) | 2011-08-12 | 2015-11-10 | Exxonmobil Chemical Patents Inc. | Polymers prepared by ring opening / cross metathesis |
CN110818525A (zh) * | 2019-11-26 | 2020-02-21 | 江西盛伟科技股份有限公司 | 一种香料青草醛的合成方法 |
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US7312331B2 (en) * | 2005-06-17 | 2007-12-25 | The Regents Of The University Of California | Stable cyclic (alkyl)(amino) carbenes as ligands for transition metal catalysts |
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2007
- 2007-04-12 FR FR0702665A patent/FR2914921A1/fr not_active Withdrawn
-
2008
- 2008-04-09 US US12/595,161 patent/US20100113791A1/en not_active Abandoned
- 2008-04-09 EP EP08736019A patent/EP2139853A1/de not_active Withdrawn
- 2008-04-09 WO PCT/EP2008/054295 patent/WO2008125568A1/fr active Application Filing
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WO2008125568A1 (fr) | 2008-10-23 |
FR2914921A1 (fr) | 2008-10-17 |
US20100113791A1 (en) | 2010-05-06 |
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