EP1351901A1 - Method for the production of aryl alkenes - Google Patents
Method for the production of aryl alkenesInfo
- Publication number
- EP1351901A1 EP1351901A1 EP01990064A EP01990064A EP1351901A1 EP 1351901 A1 EP1351901 A1 EP 1351901A1 EP 01990064 A EP01990064 A EP 01990064A EP 01990064 A EP01990064 A EP 01990064A EP 1351901 A1 EP1351901 A1 EP 1351901A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- methyl
- propanoate
- alkyl
- aryl
- benzene
- 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- Withdrawn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
- -1 aryl alkenes Chemical class 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 150000001336 alkenes Chemical class 0.000 claims abstract description 41
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 9
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 85
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 13
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 11
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 10
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 8
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 7
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 6
- 150000005840 aryl radicals Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- KBEBGUQPQBELIU-CMDGGOBGSA-N Ethyl cinnamate Chemical compound CCOC(=O)\C=C\C1=CC=CC=C1 KBEBGUQPQBELIU-CMDGGOBGSA-N 0.000 claims description 5
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229940114081 cinnamate Drugs 0.000 claims description 5
- CCRCUPLGCSFEDV-UHFFFAOYSA-N cinnamic acid methyl ester Natural products COC(=O)C=CC1=CC=CC=C1 CCRCUPLGCSFEDV-UHFFFAOYSA-N 0.000 claims description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- LUZDYPLAQQGJEA-UHFFFAOYSA-N 2-Methoxynaphthalene Chemical compound C1=CC=CC2=CC(OC)=CC=C21 LUZDYPLAQQGJEA-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- KBEBGUQPQBELIU-UHFFFAOYSA-N cinnamic acid ethyl ester Natural products CCOC(=O)C=CC1=CC=CC=C1 KBEBGUQPQBELIU-UHFFFAOYSA-N 0.000 claims description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 4
- 150000002908 osmium compounds Chemical class 0.000 claims description 4
- 150000003304 ruthenium compounds Chemical class 0.000 claims description 4
- UAIHPMFLFVHDIN-UHFFFAOYSA-K trichloroosmium Chemical compound Cl[Os](Cl)Cl UAIHPMFLFVHDIN-UHFFFAOYSA-K 0.000 claims description 4
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 claims description 3
- CCRCUPLGCSFEDV-BQYQJAHWSA-N methyl trans-cinnamate Chemical compound COC(=O)\C=C\C1=CC=CC=C1 CCRCUPLGCSFEDV-BQYQJAHWSA-N 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 2
- 125000005488 carboaryl group Chemical group 0.000 claims description 2
- 125000000068 chlorophenyl group Chemical group 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims 1
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical compound [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 241001120493 Arene Species 0.000 abstract description 16
- 238000005691 oxidative coupling reaction Methods 0.000 abstract description 13
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 description 14
- 230000001590 oxidative effect Effects 0.000 description 10
- 239000011521 glass Substances 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005859 coupling reaction Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 230000007306 turnover Effects 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 150000001491 aromatic compounds Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 5
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 238000007080 aromatic substitution reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000006254 arylation reaction Methods 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000006880 cross-coupling reaction Methods 0.000 description 3
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 229930016911 cinnamic acid Natural products 0.000 description 2
- 235000013985 cinnamic acid Nutrition 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical class [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 2
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- 238000005887 phenylation reaction Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical group C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- 150000005351 2-phenylphenols Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000744472 Cinna Species 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- 238000010485 C−C bond formation reaction Methods 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 238000005902 aminomethylation reaction Methods 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 150000005347 biaryls Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 239000006227 byproduct Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- DEHUECHFAUWOIK-UHFFFAOYSA-N furan;naphthalene Chemical compound C=1C=COC=1.C1=CC=CC2=CC=CC=C21 DEHUECHFAUWOIK-UHFFFAOYSA-N 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000003430 hydroarylation reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000000543 intermediate Substances 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
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- JFNSORWJLKDFCB-UHFFFAOYSA-N methyl 3,3-diphenylpropanoate Chemical compound C=1C=CC=CC=1C(CC(=O)OC)C1=CC=CC=C1 JFNSORWJLKDFCB-UHFFFAOYSA-N 0.000 description 1
- QTJIFBIUXXTQPC-UHFFFAOYSA-N n-(2-phenylphenyl)benzenesulfonamide Chemical class C=1C=CC=CC=1S(=O)(=O)NC1=CC=CC=C1C1=CC=CC=C1 QTJIFBIUXXTQPC-UHFFFAOYSA-N 0.000 description 1
- 150000005209 naphthoic acids Chemical class 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- WXHIJDCHNDBCNY-UHFFFAOYSA-N palladium dihydride Chemical compound [PdH2] WXHIJDCHNDBCNY-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 235000020004 porter Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002265 redox agent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000006886 vinylation reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/266—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of hydrocarbons and halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
- C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/128—Compounds comprising a halogen and an iron group metal or a platinum group metal
- C07C2527/13—Platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/20—Carbonyls
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
Definitions
- the present invention relates to a novel oxidative coupling of arenes with olefins to yield aryl alkenes, which uses ruthenium (Ru) or osmium (Os) compounds as catalysts.
- ruthenium (Ru) or osmium (Os) compounds as catalysts.
- aryl alkenes can be produced by reaction of arenes with olefins in the presence of ruthenium (Ru) or osmium (Os) compounds as catalysts.
- the reaction can be carried out in the presence of molecular oxygen as the oxidant or in the absence of 0 2 , in which case the alkene itself serves as the oxidant.
- Reasonable turnover numbers were achieved.
- the present invention thus relates to a method for the production of an aryl alkene comprising reacting an arene with an olefin in the presence of a Ru or Os compound as catalyst.
- An advantage of the process of the present invention using Ru or Os catalysts is the absence of the necessity of an acid solvent or a peroxide. Furthermore, compared to the prior art process using Rh catalysts and CO, much lower pressure of CO may be used.
- the reaction is carried out in the presence of molecular oxygen.
- a catalytic amount of hydroquinone or of a quinone such as, but not being limited to, benzoquinone, improves the yield of the reaction.
- the reaction may be carried out in an inert atmosphere but it is preferably carried out in an atmosphere containing CO.
- CO pressures are between 0 to about 100 atm, preferably between 1 to 10 and most preferably between 6 to 8 atm.
- ruthenium compounds that may be used include, but are not limited to, RuCl3»3H 2 0, [Ru(CO) 3 Cl 2 ] 2 , [ ( ⁇ 6 ⁇ C 6 H 6 )RuCl 2 ] 2 , [ ( ⁇ 6 -C 6 H 5 -Ru (H 2 0) 3 ] (F3CSO3) 2 , ⁇
- the ruthenium compound is RuCl 3* 3H 2 0.
- Preferred examples of osmium compounds that may be used according to the invention include, but are not limited to, OsCl 3 »3H 2 0, 0s0 4 , [Os(CO) 3 Cl 2 ] 2 , [ ( ⁇ 6 -C 6 H 6 ) OsCl 2 ] 2 r Os(NO)Cl 3 »5H 2 0, OS (F 3 CCOCHCOCF 3 )3 and Os 3 (CO) ⁇ 2 .
- the method of the invention is used for the production of an aryl alkene of the formula:
- Ar - CRi CR 2 - R 3 wherein Ar is an aryl radical and Ri, R 2 , R 3 independently of each other represent H, alkyl, aryl, alkoxycarbonyl or aryloxycarbonyl .
- aryl includes carboaryl radicals such as, but not being limited to, phenyl and naphthyl, and heteroaryl radicals such as, but not being limited to, furyl, thienyl, the aryl radical being optionally substituted by one or more halogen atoms, alkyl optionally substituted by one or more halogen atoms or alkoxy, and the term “arene” relates to the aromatic compound from which the aryl radical is derived, e.g., benzene, naphthalene furan, thiophene, that may be substituted as indicated for the aryl radical.
- alkyl for an alkyl radical itself or part of an alkoxy radical includes straight and branched radicals having up to 25 carbon atoms, preferably up to 20, more preferably up to 10, and most preferably up to 6 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl and hexyl, wherein said alkyl may be optionally substituted by halogen such as fluoro, chloro and bromo, or by alkoxy.
- the aromatic compound may be substituted by one or more alkyl or fluoroalkyl, preferably methyl or CF 3 , radicals, and may be, for example, toluene or xylene.
- the aromatic compound may be substituted by an alkoxy, preferably methoxy, radical, and may be, for example, anisole or 2-methoxynaphthalene.
- the aromatic compound may be substituted by a halogen such as fluoro, chloro and bromo, and may be, for example, chlorobenzene.
- Ri, R 2 , R3 are hydrogen the reaction is carried out with ethylene.
- Ri, R 2 , R3 are alkyls
- the end product will be an alkenyl arene.
- Ri, R 2 , R3 may also be alkyl substituted by one or more halogen atoms such as chloro, bromo, and preferably fluor.
- benzene is reacted with 3, 3, 4, 4, 5, 5, 6, 6-nonafluorohex-1-ene thus producing (3, 3, 4, 4, 5, 5, 6, 6-nonafluorohex-1-enyl) benzene .
- Ri is an alkoxycarbonyl radical such as ethoxycarbonyl and, more preferably, methoxycarbonyl and R 2 , R 3 are hydrogen.
- benzene is reacted with an alkyl acrylate such as methyl or ethyl acrylate.
- alkyl 2-propanoate derivatives are obtained such as methyl 3- (chlorophenyl) -2- propanoate, methyl 3-methoxyphenyl-2-propanoate, methyl 3- tolyl-2-propanoate, methyl 3- (2, 5-dimethylphenyl) -2-propanoate, methvl 3- (2-nauhthvl -2-r>ror>anoate and mp.thv] 3- (2- or 6- or 7- methoxy-2-naphthyl) -2-propanoate, that are produced by reacting an arene selected from chlorobenzene, anisole, toluene, p- xylene, naphthalene and 2-methoxynaphthalene, respectively, with methyl acrylate.
- Ri is an alkoxycarbonyl radical, preferably, methoxycarbonyl
- R 2 is hydrogen
- R 3 is a carboaryl, preferably, phenyl .
- an arene is reacted with an alkyl cinnamate such as methyl or ethyl cinnamate.
- benzene is reacted with methyl cinnamate, thus producing methyl 3,3-diphenyl propanoate.
- Oxygen is preferably added to the reaction at 0-10 atmospheres, more preferably 1-2 atmospheres, and the temperature of the reaction is preferably 50-250 °C, and more preferably 150-180 °C. At temperatures above 250 °C, the reaction will still take place, but some amount of decomposition will result. At lower than 50 °C, the reaction will still take place, but the turnover will become unproductively small. Similarly, at an 0 2 pressure above 10 atm, the reaction will still be expected to take place, but the process would not be industrially practical.
- aryl alkenes produced by the process of the invention are useful intermediates particularly for the pharmaceutical industry.
- the present invention provides a novel oxidative coupling of arenes with olefins, which may optionally use molecular oxygen as the oxidant.
- Good catalytic activity is exhibited by the Ru compounds RuCl 3 »3H 2 0, [Ru (CO) 3 C1 2 ] 2, [ ( ⁇ 6 - C 6 H 6 )RuCl 2 ]2, Ru(NO)Cl 3 »5H 2 0 and Ru (F3CCOCHCOCF3) 3 under a pressure of 2 atm of 0 2 and 6.1 atm of CO at 180°C.
- the alkene itself serves as the oxidant and the coupling is accompanied by a parallel alkene hydrogenation.
- the reaction is accelerated by electron donating substituents on the arene.
- the dehydrogenative coupling proceeds either under 0 2 (Equation 1) or in an inert atmosphere (Equation 2) .
- the product turnover number increases with CO pressure up to
- Alky acrylates are by far the most active of the olefins tested.
- Example 1 Oxidative Coupling of Benzene with Acrylate Esters
- Fischer-Porter glass reactor was pressurized with 6.1 atm CO and 2 atm O 2 and heated to 180°C with stirring for 48 hours, thus producing methyl or ethyl cinnamate.
- the results are shown in Table 1.
- Addition of a catalytic amount of hydroquinone (HQ) (Entries 6 and 7) or quinone improved the yield the turnover number and the mass balance of the reaction.
- Ten or 20 eq of HQ (relative to Ru) had a similar effect.
- Addition of a radical trap (galvinoxyl) does not retard the reaction and it proceeds as well in the dark (Entry 3 in Table 1) .
- Entry 5 was carried out under 3.4 atm of CO and 3.4 atm of ethylene.
- (E) is defined according to Stretweiser et al (1972) . [0030] The reaction is accelerated by electron donating substituents on the arene.
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Abstract
The present invention relates to a novel oxidative coupling arenes with olefins to yield aryl alkenes, which uses ruthenium (Ru) or Osmium (Os) compounds as catalysts.
Description
METHOD FOR THE PRODUCTION OF ARYL ALKENES FIELD OF THE INVENTION [0001] The present invention relates to a novel oxidative coupling of arenes with olefins to yield aryl alkenes, which uses ruthenium (Ru) or osmium (Os) compounds as catalysts.
BACKGROUND OF THE INVENTION [0002] Catalytic carbon-carbon bond formation by C-H activation is a topic of much current interest. Significant progress has been made in recent years in the development of synthetically useful catalytic addition of arenes to alkenes to give the saturated alkyl arenes (Murai et al, 1993; Kakiuchi et al, 1996; Jia et al, 2000a,' 2000b; Matsumoto et al, 2000a) .
[0003] Catalytic oxidative coupling of arenes with alkenes to give aryl alkenes, in which the double bond is preserved, is a highly desirable goal. Such a reaction, which does not require the utilization of a reactive substituent, and does not produce waste, may have an advantage over other methods for the preparation of aromatic alkenes, such as the well-known Heck reaction for the vinylation of aryl halides. Stoichiometric coupling of olefins with arenes promoted by Pd(II) is well known (Moritani et al, 1967; US Patent No. 3,674,884, 1972).
[0004] Tsuji et al (1984) and lately Fujiwara et al (1996) and Mikami et al (1999) have demonstrated catalysis by utilizing peroxides as oxidants in their systems. While good catalytic activity was achieved with some alkenes, acrylates resulted in low activity (~10 turnovers) . The use of peroxide oxidants and acetic acid solvent in these systems is problematic from the industrial point of view. Attempts to use 02 or air resulted in low activity in intramolecular (Miura et al, 1997, 1998) and inter olecular (Fujiwara et al, 1969, 1976; Asano et al, 1970; Shue, 1972; US Patent No. 3,855,329) coupling and alkene oxidation took place in the intermolecular reaction.
[0005] Another approach utilizing Rh carbonyl clusters under high (20-30 at ) CO pressure (Hong et al, 1984) resulted in modest catalytic activity with concomitant hydrocarbonylation of the alkene. Low catalytic activity was reported for the Rh- catalyzed photochemical coupling of arenes with alkenes, in which concomitant hydrogenation of the alkene took place and biaryls were formed as by-products (Sasaki et al, 1988; JP 1193241) . A very low yield Rh catalyzed oxidative phenylation of ethylene to styrene was reported (Matsumoto et al, 2000b; US Patent No. 6,127,590).
SUMMARY OF THE INVENTION [0006] It has now been found according to the present invention that aryl alkenes can be produced by reaction of arenes with olefins in the presence of ruthenium (Ru) or osmium (Os) compounds as catalysts. The reaction can be carried out in the presence of molecular oxygen as the oxidant or in the absence of 02, in which case the alkene itself serves as the oxidant. Reasonable turnover numbers were achieved.
[0007] The present invention thus relates to a method for the production of an aryl alkene comprising reacting an arene with an olefin in the presence of a Ru or Os compound as catalyst. An advantage of the process of the present invention using Ru or Os catalysts is the absence of the necessity of an acid solvent or a peroxide. Furthermore, compared to the prior art process using Rh catalysts and CO, much lower pressure of CO may be used.
[0008] In one embodiment, the reaction is carried out in the presence of molecular oxygen. The addition of a catalytic amount of hydroquinone or of a quinone such as, but not being limited to, benzoquinone, improves the yield of the reaction. The reaction may be carried out in an inert atmosphere but it is preferably carried out in an atmosphere containing CO. CO pressures are between 0 to about 100 atm, preferably between 1 to 10 and most preferably between 6 to 8 atm.
[0009] While it is expected that any ruthenium or osmium compound could be used in accordance with the present invention, preferred examples of ruthenium compounds that may be used include, but are not limited to, RuCl3»3H20, [Ru(CO)3Cl2]2, [ (η6~C6H6)RuCl2]2, [ (η6-C6H5-Ru (H20) 3] (F3CSO3) 2, ■
Ru (NO) C13«5H20, Ru(F3CCOCHCOCF3)3 and Ru3(CO)ι2. In one preferred embodiment, the ruthenium compound is RuCl3*3H20.
[0010] Preferred examples of osmium compounds that may be used according to the invention include, but are not limited to, OsCl3»3H20, 0s04, [Os(CO)3Cl2]2, [ (η6-C6H6) OsCl2] 2r Os(NO)Cl3»5H20, OS (F3CCOCHCOCF3)3 and Os3(CO)ι2.
[0011] Most of the Ru and Os compounds present a higher catalytic activity in a CO atmosphere but the compounds Ru(F3CCOCHCOCF3) 3,Ru3(CO)i2 and Os3(CO)12 exhibit catalytic activity in the absence of a CO atmosphere.
[0012] In one embodiment, the method of the invention is used for the production of an aryl alkene of the formula:
Ar - CRi = CR2 - R3 wherein Ar is an aryl radical and Ri, R2, R3 independently of each other represent H, alkyl, aryl, alkoxycarbonyl or aryloxycarbonyl .
[0013] As used herein, the term "aryl" includes carboaryl radicals such as, but not being limited to, phenyl and naphthyl, and heteroaryl radicals such as, but not being limited to, furyl, thienyl, the aryl radical being optionally substituted by one or more halogen atoms, alkyl optionally substituted by one or more halogen atoms or alkoxy, and the term "arene" relates to the aromatic compound from which the aryl radical is derived, e.g., benzene, naphthalene furan, thiophene, that may be substituted as indicated for the aryl radical.
[0014] As used herein, the term "alkyl" for an alkyl radical itself or part of an alkoxy radical includes straight and
branched radicals having up to 25 carbon atoms, preferably up to 20, more preferably up to 10, and most preferably up to 6 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl and hexyl, wherein said alkyl may be optionally substituted by halogen such as fluoro, chloro and bromo, or by alkoxy.
[0015] In one embodiment, the aromatic compound may be substituted by one or more alkyl or fluoroalkyl, preferably methyl or CF3, radicals, and may be, for example, toluene or xylene. In another embodiment, the aromatic compound may be substituted by an alkoxy, preferably methoxy, radical, and may be, for example, anisole or 2-methoxynaphthalene. In a further embodiment, the aromatic compound may be substituted by a halogen such as fluoro, chloro and bromo, and may be, for example, chlorobenzene. [0016] When Ri, R2, R3 are hydrogen the reaction is carried out with ethylene. Thus when the arene is benzene the end product is styrene and when the arene is naphthalene the end product is vinylnaphthalene. When Ri, R2, R3 are alkyls, the end product will be an alkenyl arene. Ri, R2, R3 may also be alkyl substituted by one or more halogen atoms such as chloro, bromo, and preferably fluor. In one example as shown herein benzene is reacted with 3, 3, 4, 4, 5, 5, 6, 6-nonafluorohex-1-ene thus producing (3, 3, 4, 4, 5, 5, 6, 6-nonafluorohex-1-enyl) benzene . [0017] In one preferred embodiment of the invention Ri is an alkoxycarbonyl radical such as ethoxycarbonyl and, more preferably, methoxycarbonyl and R2, R3 are hydrogen. Thus for the preparation of an alkyl cinna ate, benzene is reacted with an alkyl acrylate such as methyl or ethyl acrylate. When a substituted benzene or naphthalene compound is reacted with an alkyl acrylate, the corresponding alkyl 2-propanoate derivatives are obtained such as methyl 3- (chlorophenyl) -2- propanoate, methyl 3-methoxyphenyl-2-propanoate, methyl 3- tolyl-2-propanoate, methyl 3- (2, 5-dimethylphenyl) -2-propanoate, methvl 3- (2-nauhthvl -2-r>ror>anoate and mp.thv] 3- (2- or 6- or 7-
methoxy-2-naphthyl) -2-propanoate, that are produced by reacting an arene selected from chlorobenzene, anisole, toluene, p- xylene, naphthalene and 2-methoxynaphthalene, respectively, with methyl acrylate. [0018] In another preferred embodiment of the invention Ri is an alkoxycarbonyl radical, preferably, methoxycarbonyl, R2 is hydrogen and R3 is a carboaryl, preferably, phenyl . Thus for the preparation of an alkyl 3,3-diaryl propanoate, an arene is reacted with an alkyl cinnamate such as methyl or ethyl cinnamate. In one example as shown herein benzene is reacted with methyl cinnamate, thus producing methyl 3,3-diphenyl propanoate.
[0019] Oxygen is preferably added to the reaction at 0-10 atmospheres, more preferably 1-2 atmospheres, and the temperature of the reaction is preferably 50-250 °C, and more preferably 150-180 °C. At temperatures above 250 °C, the reaction will still take place, but some amount of decomposition will result. At lower than 50 °C, the reaction will still take place, but the turnover will become unproductively small. Similarly, at an 02 pressure above 10 atm, the reaction will still be expected to take place, but the process would not be industrially practical.
[0020] The aryl alkenes produced by the process of the invention are useful intermediates particularly for the pharmaceutical industry.
DETAILED DESCRIPTION OF THE INVENTION [0021] The present invention provides a novel oxidative coupling of arenes with olefins, which may optionally use molecular oxygen as the oxidant. Good catalytic activity is exhibited by the Ru compounds RuCl3»3H20, [Ru (CO) 3C12] 2, [ (η6- C6H6)RuCl2]2, Ru(NO)Cl3»5H20 and Ru (F3CCOCHCOCF3) 3 under a pressure of 2 atm of 02 and 6.1 atm of CO at 180°C. In the absence of 02, the alkene itself serves as the oxidant and the
coupling is accompanied by a parallel alkene hydrogenation.
The reaction is accelerated by electron donating substituents on the arene.
[0022] Notably, the dehydrogenative coupling proceeds either under 02 (Equation 1) or in an inert atmosphere (Equation 2) .
In absence of 02 the olefin itself serves as an oxidant and, for example, when benzene (Ar = phenyl) is reacted with methyl acrylate (Ri, is -COOCH3, R2, R3 = H) a 1:1 ratio of cinnamate: propanoate is obtained. In comparison, under 2 atm of 02 the cinnamate yield is doubled and a ratio of about 3:1 of cinnamate: 2-propanoate is obtained (see Table 1).
Essentially no organic carbonylation products are observed.
The product turnover number increases with CO pressure up to
6.1 atm, beyond which further pressure increase has no beneficial effect. Various arenes and alkenes are reactive
(see Table 3) . Alky acrylates are by far the most active of the olefins tested.
Ri R2 Ru or Os catalyst t* R _ /R'2
Ar-H + HJ-<R3 - AA s 2 + ^R3 (2)
[0023] The invention will now be illustrated by the following non-limiting Examples. Example 1: Oxidative Coupling of Benzene with Acrylate Esters
1A. With Ru Complexes as Catalysts
[0024] A solution containing 8 ml of benzene, 0.02 mmol of RuCl3»3H20 (1) and 5 mmol of methyl or ethyl acrylate in a
Fischer-Porter glass reactor was pressurized with 6.1 atm CO and 2 atm O2 and heated to 180°C with stirring for 48 hours, thus producing methyl or ethyl cinnamate. The results are shown in Table 1.
[0025] Addition of a catalytic amount of hydroquinone (HQ) (Entries 6 and 7) or quinone improved the yield the turnover number and the mass balance of the reaction. Ten or 20 eq of HQ (relative to Ru) had a similar effect. Addition of a radical trap (galvinoxyl) does not retard the reaction and it proceeds as well in the dark (Entry 3 in Table 1) .
Table 1 Oxidative Coupling of Benzene with Acrylate Esters
Reaction conditions: a solution containing 8 mL of benzene, 0.02 mmol of 1 and 5 mmol of acrylate ester in a Fischer-Porter glass reactor is pressurized with 6.1 atm CO and 2 atm 02 and heated to 180°C with stirring for 48 hours. *MA = methyl acrylate. **EA = ethyl acrylate. TON = turnover number. Yields are based on acrylate ester.
IB. With [η6-C6H6-Ru(H20)3] (F3CS03)2 as Catalyst with 1 atm of CO
[0026] A solution containing 8 ml of benzene, 0.02 mmol of [η6-C6H6-Ru(H20)3] (F3CS03)2 and 5 mmol of ethyl acrylate in a Fischer-Porter glass reactor was pressurized with 1 atm CO and
7.1 atm of inert gas (e.g., Argon or N2) and heated to 180°C with stirring for 48 hours. GC analysis revealed formation of 1.1 mmol (E) -ethyl cinnamate (22% yield, 55 TON) and 1.3 mmol ethyl propanoate (26% yield, 65 TON) .
lC. With Ru(CF3C0CHC0CF3)3 or 0s3(C0)ι2 or Ru3 (CO) 12 as Catalysts without CO Pressure
[0027] A solution containing 8 ml of benzene, 0.02 mmol of catalyst (per metal center) and 5 mmol of ethyl acrylate in a Fischer-Porter glass reactor was pressurized with 2 atm of 02 and 6.1 atm of inert gas (e.g., Argon or N2) and heated to 180°C with stirring for 48 hours. The results are shown in Table 2.
Table 2 Oxidative Coupling of Benzene with Acrylate Esters without CO
Pressure*'*3
a Reaction conditions: a solution containing 8 mL of benzene, 0.02 mmol of catalyst (per metal center) and 5 mmol of ethyl acrylate in a Fischer-Porter glass reactor is pressurized with 6.1 atm Ar and 2 atm 02 and heated to 180°C with stirring for 48 hours. Yields are based on ethyl acrylate. b Other catalysts mentioned above gave under this conditions about 1 TON.
ID. With Os Complexes as Catalysts [0028] A solution containing 8 ml of benzene, 0.02 mmol of OsCl3»xH20 (2) or Os04 (3) and 5 mmol of ethyl acrylate in a
Fischer-Porter glass reactor was pressurized under 2 atm of 02 and 6.1 atm of argon and heated to 180°C with stirring for 48 hours, thus producing ethyl cinnamate. The results are shown in Table 3.
Table 3 Oxidative Coupling of Benzene with Ethyl Acrylate Utilizing Os
Compounds
a Reaction conditions: a solution containing 8 mL of benzene,
0.02 mmol of 2 or 3 and 5 mmol of ethyl acrylate in a Fischer- Porter glass reactor is pressurized with CO and 02 and heated to 180°C with stirring for 48 hours. Yields are based on acrylate ester. Example 2 Oxidative Coupling of Various Arenes with Olefins under Q2
[0029] In a typical reaction protocol, an 80 mL glass pressure tube is charged with 90 mmol of arene, 0.02 mmol of RuCl3«3H20, 0.2 mmol HQ and 5 mmol of acrylate. The reactor is then evacuated and then pressurized with 6.1 atm CO and 2 atm 02 and heated to 180 °C with stirring for 48 hours. The liquid phase is sampled and analyzed by gas chromatography, mass spectroscopy and HNMR spectroscopy at the end of the reaction. The products are characterized by comparison with authentic samples. In this way, methyl acrylate was reacted with benzene, chlorobenzene, toluene, anisole, p-xylene, naphthalene and 2-methoxynaphthalene, and ethylene, methyl cinnamate and H2C=CH (CF2) 3CF3 were reacted with benzene. The results are shown in Table 4.
Table 4 Oxidative Coupling of Various Arenes with Olefins under Oa a
The reaction was carried out as described above in Example 2.
Entry 5 was carried out under 3.4 atm of CO and 3.4 atm of ethylene. In Entry 6, 2.63 mmol of H2C=CH (CF2) 3CF3 were used.
(E) is defined according to Stretweiser et al (1972) . [0030] The reaction is accelerated by electron donating substituents on the arene.
[0031] In summary, a novel Ru- and Os-catalyzed oxidative coupling of arenes with olefins to produce aryl alkenes, which can either directly utilize dioxygen or can utilize the alkene as oxidant and results in reasonable turnover numbers, has been disclosed..
REFERENCES
Asano et al, "Aromatic substitution of olefins. Reaction of ferrocene with styrene in the presence of palladium (II) acetate", J Chem Commun 1293 (1970) Fujiwara et al, "Aromatic substitution of olefins. VI.
Arylation of olefins with palladium (II) acetate", J Am Chem Soc 91:7166 (1969)
Fujiwara et al, "Aromatic substitution of olefins. XXV.
Reactivity of benzene, naphthalene, ferrocene, and furan toward styrene, and the substituent effect on the reaction of monosubstituted benzenes with styrene", J Org Chem 41:1681 (1976)
Fujiwara 'et al, "Exploitation of synthetic reactions via C-H bond activation by transition metal catalysts. Carboxylation and aminomethylation of alkanes or arenes", Synlett 591 (1996)
Hong et al, "Rhodium carbonyl-catalyzed activation of carbon- hydrogen bonds for application in organic synthesis. V. Phenylation of olefins with benzenes", J Mol Catal 297 (1984)
Jia et al, "Efficient activation of aromatic C-H bonds for addition to C-C multiple bonds", Science 287:1992 (2000a)
Jia et al, "Novel Pd(II)- and Pt (II) -catalyzed regio- and stereoselective trans-hydroarylation of alkynes by simple arenes", J Am Chem Soc 122:7252 (2000b)
Kakiuchi et al, "Ruthenium-catalyzed addition of aromatic i ines at the ortho C-H bonds to olefins", Chem Lett 111 (1996)
Masato et al, Japanese patent 1193241A2, "Production of Cinnamic Acid Ester Derivative", August 3, 1989
Matsumoto et al, "Anti-Markovnikov Olefin Arylation Catalyzed by an Iridium Complex", J Am Chem Soc 122:7414 (2000a)
Matsumoto et al, "Oxidative arylation of ethylene with benzene to produce styrene" Chem Lett 9:1064-1065 (2000b) Mikami et al, "Catalytic C-H bond activation-asymmetric olefin coupling reaction: the first example of asymmetric Fujiwara-Moritani reaction catalyzed by chiral palladium(II) complexes", Chem Lett 55 (1999)
Miura et al, "Palladium-catalyzed oxidative cross-coupling of 2-phenylphenols with alkenes", Chem Lett 1103 (1997)
Miura et al, "Oxidative Cross-Coupling of N- (1, 1 ' -biphenyl-2- yl) benzenesulfonamides or Benzoic and Naphthoic Acids with Alkenes Using a Palladium-Copper Catalyst System under Air", J Org Chem 63:5211 (1998)
Moritani et al, "Aromatic substitution of styrene-palladium chloride complex", Tetrahedron Lett 1119 (1967)
Moritani et al, US Patent 3,674,884, "Process for the Preparation of Aromatic Hydrocarbons Containing
Monoethylenic Unsaturated Radicals", July 4, 1972
Murai et al, "Efficient Catalytic Addition of Aromatic Carbon- Hydrogen Bonds to Olefin" Nature 366:529 (1993)
Sasaki et al, "Carbon-carbon double bond insertion in catalytic carbon-hydrogen activation. Dehydrogenative cross- coupling of arenes with olefins", Chem Lett 4:685-688 (1988)
Shue RS "Reactions of aromatics and olefins catalyzed by homogeneous palladium (II) compounds under oxygen", J Catal 26:112 (1972)
Shue, RS, US Patent 3,855,329, "Olefin Coupling in the Presence of Palladium Carboxylates", December 17, 1974
Stretweiser et al, Introduction to Organic Chemistry, 4th. Ed., Prentice-Hall Inc., New Jersey (1992), p. 54 Tanaka et al, Japanese patent 01193241 A2, "Production of Cinnamic Acid Ester Derivative", August 3, 1989
Taube et al, US Patent 6,127,590, "Oxidative Coupling of Olefins and Aromatics Using a Rhodium Catalyst and a Copper (II) Redox Agent", October 3, 2000 Tsuji et al, "Palladium-catalyzed oxidative coupling of aromatic compounds with olefins using tert-butyl perbenzoate as a hydrogen acceptor", Tetrahedron 40:2699 (1984)
Claims
1. A method for the production of an aryl alkene comprising reacting an arene with an olefin in the presence of a Ru or Os compound as catalyst.
2. A method according to claim 1, wherein the reaction is carried out in the presence of molecular oxygen.
3. A method according to claim 2, wherein the reaction is carried out in the presence of a hydroquinone or a quinone .
4. A method according to any one of claims 1 to 3, wherein the reaction is carried out in an atmosphere containing CO .
5. A method according to claim 4, wherein the CO atmosphere has a CO pressure of up to about 100 atm.
6. A method according to claim 5, wherein said CO pressure is 6-8 atm.
7. A method according to any one of claims 1 to 6, wherein the ruthenium compound is selected from the group consisting of RuCl3»3H20, [Ru (CO) 3C12] 2, [ (ηs-C6H6) RuCl2] 2, _ (η6- C6Hs-Ru(H20)3] (F3CS03)2, Ru (NO) C13»5H20, Ru (F3CCOCHCOCF3) 3 and Ru3(CO)12.
8. The method according to claim 7, wherein the ruthenium compound is RuCl3*3H2θ.
9. A method according to any one of claims 1 to 6, wherein the osmium compound is selected from the group consisting of OsCl3»xH20, [Os (CO) 3C12] 2, [ (η6-C6H6) OsCl2] 2,
Os (NO) C13»5H20, Os (F3CCOCHCOCF3) 3 and Os04.
10. The method according to claim 9, wherein the osmium compound is OsCl3»xH20.
11. A method according to any one of claims 1 to 10, for the production of an aryl alkene of the formula:
Ar - CRi = CR2 - R3 wherein Ar is an aryl radical and Ri, R2, R3 independently of each other represent H, alkyl, aryl, alkoxycarbonyl or aryloxycarbonyl .
12. A method according to claim 11 wherein Ar is a carboaryl such as phenyl and naphthyl, or a heteroaryl radical such as furyl, thienyl, the aryl radical being optionally substituted by one or more halogen atoms, alkyl optionally substituted by one or more halogen atoms or alkoxy.
13. A method according to claim 12 wherein said alkyl or alkoxy radical has up to 25 carbon atoms, preferably up to 20, more preferably up to 10, and most preferably up to 6 carbon atoms .
14. A method according to any one of claims 1 to 13 for the preparation of an alkyl cinnamate which comprises reacting benzene with an alkyl acrylate.
15. A method according to claim 14 for the preparation of methyl cinnamate which comprises reacting benzene with methyl acrylate.
16. A method according to claim 14 for the preparation of ethyl cinnamate which comprises reacting benzene with ethyl acrylate.
17. A method according to any one of claims 1 to 13 for the preparation of an alkyl aryl-2-propanoate which comprises reacting an arene with an alkyl acrylate.
18. A method according to claim 17 for the preparation of an alkyl aryl-2-propanoate selected from methyl 3- (chlorophenyl) -2-propanoate, methyl 3- (methoxyphenyl) -2- propanoate, methyl 3- (tolyl) -2-propanoate, methyl 3- (2, 5- dimethylphenyl) 2-propanoate, methyl 3- (2-naphthyl) - 2- propanoate and methyl 3- (2- or 6- or 7-methoxy-2-naphthyl) -2- propanoate, which comprises reacting an arene selected from chlorobenzene, anisole, toluene, p-xylene, naphthalene and 2- methoxynaphthalene, respectively, with methyl acrylate.
19. A method according to any one of claims 1 to 13 for the preparation of styrene which comprises reacting benzene with ethylene.
20. A method according to any one of claims 1 to 13 for the preparation of (3, 3, , 4, 5, 5, 6, 6, 6-nonafluoro-hex-l- enyl) benzene which comprises reacting benzene with H2C=CH (CF2)3CF3.
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| IL14027500 | 2000-12-13 | ||
| IL14027500A IL140275A0 (en) | 2000-12-13 | 2000-12-13 | Method for the production of aryl alkenes |
| PCT/US2001/047570 WO2002055455A1 (en) | 2000-12-13 | 2001-12-13 | Method for the production of aryl alkenes |
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2001
- 2001-12-13 WO PCT/US2001/047570 patent/WO2002055455A1/en not_active Ceased
- 2001-12-13 EP EP01990064A patent/EP1351901A4/en not_active Withdrawn
-
2003
- 2003-06-12 IL IL156421A patent/IL156421A/en not_active IP Right Cessation
Non-Patent Citations (2)
| Title |
|---|
| No further relevant documents disclosed * |
| See also references of WO02055455A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| IL140275A0 (en) | 2002-02-10 |
| IL156421A (en) | 2011-06-30 |
| EP1351901A4 (en) | 2006-05-31 |
| WO2002055455A1 (en) | 2002-07-18 |
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