TW201800376A - 用於形成多炔基-芳烴的方法 - Google Patents
用於形成多炔基-芳烴的方法 Download PDFInfo
- Publication number
- TW201800376A TW201800376A TW105122952A TW105122952A TW201800376A TW 201800376 A TW201800376 A TW 201800376A TW 105122952 A TW105122952 A TW 105122952A TW 105122952 A TW105122952 A TW 105122952A TW 201800376 A TW201800376 A TW 201800376A
- Authority
- TW
- Taiwan
- Prior art keywords
- aromatic compound
- alkyne
- fluorosulfonate
- group
- alkyl
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 23
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 68
- -1 arene compounds Chemical class 0.000 claims abstract description 48
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 47
- 125000003118 aryl group Chemical group 0.000 claims description 70
- 125000000217 alkyl group Chemical group 0.000 claims description 52
- 239000003054 catalyst Substances 0.000 claims description 41
- 239000011541 reaction mixture Substances 0.000 claims description 40
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 34
- 239000003446 ligand Substances 0.000 claims description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 22
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 125000004429 atom Chemical group 0.000 claims description 12
- 150000004699 copper complex Chemical class 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 10
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 10
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 claims description 8
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 6
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 claims description 6
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- SXWIAEOZZQADEY-UHFFFAOYSA-N 1,3,5-triphenylbenzene Chemical compound C1=CC=CC=C1C1=CC(C=2C=CC=CC=2)=CC(C=2C=CC=CC=2)=C1 SXWIAEOZZQADEY-UHFFFAOYSA-N 0.000 claims description 5
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 claims description 5
- HQUHRVJSRBAPTC-UHFFFAOYSA-N C1(=CC=CC2=CC=CC=C12)C1(C2=CC=CC=C2CC=2C=CC=CC12)C1=CC=CC2=CC=CC=C12 Chemical compound C1(=CC=CC2=CC=CC=C12)C1(C2=CC=CC=C2CC=2C=CC=CC12)C1=CC=CC2=CC=CC=C12 HQUHRVJSRBAPTC-UHFFFAOYSA-N 0.000 claims description 5
- XBDYBAVJXHJMNQ-UHFFFAOYSA-N Tetrahydroanthracene Natural products C1=CC=C2C=C(CCCC3)C3=CC2=C1 XBDYBAVJXHJMNQ-UHFFFAOYSA-N 0.000 claims description 5
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- QBHWPVJPWQGYDS-UHFFFAOYSA-N hexaphenylbenzene Chemical compound C1=CC=CC=C1C(C(=C(C=1C=CC=CC=1)C(C=1C=CC=CC=1)=C1C=2C=CC=CC=2)C=2C=CC=CC=2)=C1C1=CC=CC=C1 QBHWPVJPWQGYDS-UHFFFAOYSA-N 0.000 claims description 5
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 claims description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 5
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 claims description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 3
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 claims description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- VHMICKWLTGFITH-UHFFFAOYSA-N 2H-isoindole Chemical compound C1=CC=CC2=CNC=C21 VHMICKWLTGFITH-UHFFFAOYSA-N 0.000 claims description 3
- FCNCGHJSNVOIKE-UHFFFAOYSA-N 9,10-diphenylanthracene Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 FCNCGHJSNVOIKE-UHFFFAOYSA-N 0.000 claims description 3
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 3
- XQJHRCVXRAJIDY-UHFFFAOYSA-N aminophosphine Chemical compound PN XQJHRCVXRAJIDY-UHFFFAOYSA-N 0.000 claims description 3
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 claims description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- 150000003852 triazoles Chemical class 0.000 claims description 3
- 150000001735 carboxylic acids Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 claims description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- HLIBJQGJVDHCNB-UHFFFAOYSA-N benzylsulfamide Chemical compound C1=CC(S(=O)(=O)N)=CC=C1NCC1=CC=CC=C1 HLIBJQGJVDHCNB-UHFFFAOYSA-N 0.000 claims 1
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 claims 1
- 150000001879 copper Chemical class 0.000 claims 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 claims 1
- 125000001475 halogen functional group Chemical group 0.000 claims 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 abstract description 31
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical group [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 abstract description 19
- 230000008878 coupling Effects 0.000 abstract description 16
- 238000010168 coupling process Methods 0.000 abstract description 16
- 238000002360 preparation method Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 45
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 229910052799 carbon Inorganic materials 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 23
- 239000002585 base Substances 0.000 description 22
- 229910052739 hydrogen Inorganic materials 0.000 description 22
- 239000010410 layer Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 235000019439 ethyl acetate Nutrition 0.000 description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 15
- 238000002390 rotary evaporation Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 0 *c(c(C#C*)c(*)c(C#C*)c1*)c1C#C* Chemical compound *c(c(C#C*)c(*)c(C#C*)c1*)c1C#C* 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 244000205754 Colocasia esculenta Species 0.000 description 8
- 235000006481 Colocasia esculenta Nutrition 0.000 description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 7
- BHBIPLOIWQSVID-UHFFFAOYSA-N thiohypofluorous acid Chemical compound SF BHBIPLOIWQSVID-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000000304 alkynyl group Chemical group 0.000 description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 125000006577 C1-C6 hydroxyalkyl group Chemical group 0.000 description 5
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 5
- 239000012267 brine Substances 0.000 description 5
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 4
- KUZBIUTZPWIHSI-UHFFFAOYSA-N 3,5-diethynylbenzoic acid Chemical compound OC(=O)C1=CC(C#C)=CC(C#C)=C1 KUZBIUTZPWIHSI-UHFFFAOYSA-N 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 4
- 239000013058 crude material Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- KHFKMSRXJISUIA-UHFFFAOYSA-N methyl 3,5-bis(fluorosulfonyloxy)benzoate Chemical compound FS(=O)(=O)OC=1C=C(C(=O)OC)C=C(C=1)OS(=O)(=O)F KHFKMSRXJISUIA-UHFFFAOYSA-N 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Chemical group 0.000 description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229920001197 polyacetylene Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 4
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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Abstract
一種使具有兩個或更多個氟磺酸酯取代基的芳族化合物與炔烴偶合的方法,其適用於製備多炔基取代之芳烴化合物。
Description
本發明係關於形成特定經取代之芳族化合物且更具體言之係關於形成多炔基-芳烴。
薗頭偶合(Sonogashira coupling)為用於偶合芳族化合物與炔烴,由此在芳族化合物與炔烴之間形成新碳-碳鍵的有價值的合成方法。一種常見薗頭偶合反應使用鹵基取代之芳族化合物作為起始物質。另一常見偶合反應使用羥基取代之芳族化合物。
已知具有式F3CSO3-的三氟甲磺酸根可用於在薗頭偶合反應中置換鹵化物,然而三氟甲磺酸酐((CF3SO2)2O)的消耗限制薗頭偶合中使用三氟甲磺酸鹽製造精細化學物質。另外,三氟甲磺酸酐的原子經濟性低,因為在酚系起始物質官能化之後,一半分子以單體三氟甲磺酸根陰離子(CF3SO3 -)形式消耗。在一些情況下,涉及三氟甲磺酸鹽的薗頭偶合反應在鹼性條件下展現對水的敏感性。
甲烷磺酸芳酯亦適於薗頭偶合反應,但缺點為需要昂貴的鈀催化劑。使用甲烷磺酸芳酯的另一缺點為低原子經濟性。
當使用三氟甲磺酸根或甲烷磺酸根部分進行薗
頭偶合時,通常分兩步驟進行反應,第一步驟包括用三氟甲磺酸根或甲烷磺酸根置換芳族化合物上的羥基,且第二步驟包括使芳族化合物與炔烴偶合。第一及第二步驟之間一般需要分離步驟。
多炔基取代之芳烴適用作狄爾斯-阿爾德聚合(Diels-Alder polymerization)中的單體來形成聚伸苯基聚合物。2015年8月18日申請且讓渡給與本申請案相同的受讓人的美國專利申請案第62/206,343號揭示一種使用薗頭偶合形成芳族炔烴的改良方法。然而,本申請案未能揭示多炔基取代之芳烴的形成。需要一種使用薗頭偶合形成多炔基取代之芳烴的方法,所述方法不使用三氟甲磺酸鹽或甲烷磺酸鹽。
本發明提供一種形成多炔基取代之芳烴化合物的方法,其包括:(a)使多羥基取代之芳族化合物與氟磺化劑反應形成多(氟磺酸酯)取代之芳族化合物;以及(b)使多(氟磺酸酯)取代之芳族化合物與炔烴在催化劑存在下在使炔烴與多(氟磺酸酯)取代之芳族化合物有效偶合的條件下反應且形成多炔基取代之芳烴化合物;其中催化劑包括一個或多個第10族原子或銅錯合物。
本發明亦提供一種形成多炔基取代之芳烴化合物的方法,其包括:(a)使具有兩個或更多個氟磺酸酯取代基的芳族化合物;以及(b)使具有兩個或更多個氟磺酸酯取代基的芳族化合物與炔烴在反應混合物中在使炔烴與芳族化合物有效偶合的條件下反應且形成多炔基取代之芳烴化合物,所述反應混合物包括催化劑,所述催化劑包括一個或多
個第10族原子或銅錯合物。
如本說明書通篇所使用,除非上下文另外明確指示,否則以下縮寫將具有以下含義:℃=攝氏度;g=公克;mg=毫克;mmol=毫莫耳;L=公升;mL=毫升;mmHg=毫米汞柱;Pa=帕斯卡;1mmHg=133.3Pa;min.=分鐘;hr.=小時;DI=去離子;Da=道爾頓;以及NMR=核磁共振。除非另外規定,否則全部量均為重量百分比(「重量%」)且全部比率均為莫耳比。所有數值範圍均為包含性的且可按任何次序組合,除非很明顯此類數值範圍限於總計為100%。冠詞「一(a)」、「一(an)」以及「所述」係指單數及複數。當一個元件稱為「安置於」另一元件「上」時,其可直接在另一元件上或其間可能存在插入元件。相比之下,當元件稱為「直接安置於」另一元件「上」時,不存在插入元件。
「鹵基」係指氟、氯、溴以及碘。術語「烷基」係指烷烴基,且包含烷烴單基、二基(伸烷基)及較高碳數基團。除非另外規定,否則「烷基」係指直鏈、分支鏈以及環狀烷基。術語「雜烷基」係指用一個或多個雜原子(諸如氮、氧、硫、磷)置換基團內的一個或多個碳原子的烷基,例如醚或硫醚。若任何烷基或雜烷基未指明碳數目,則預期1-12個碳。術語「烯基」係指烯烴基,且包含烯烴單基、二基(伸烯基)及較高碳數基團。除非另外規定,否則「烯基」
係指直鏈、分支鏈以及環狀烯基。術語「炔基」係指炔烴基,且包含炔烴單基、二基及較高碳數基團。「炔基」係指直鏈及分支鏈炔基。若任何烯基或炔基未指明碳數目,則預期2-12個碳。
術語「芳烴」及「芳族化合物」可互換使用。如本文所用,「芳族化合物」係指具有一個或多個芳基部分的化合物。「芳基」部分係指自芳族環衍生的任何官能團或取代基。亦如本文所用,術語「芳基」及「芳族」分別包含「雜芳基」及「雜芳族」。芳基部分含有4n+2個π電子,其中n為整數。「雜芳基」及「雜芳族」係指衍生自芳族環且具有至少一個選自氮、氧及硫的雜原子的任何官能團或取代基。
本發明提供一種形成多炔基取代之芳烴化合物的方法,其包括:(a)使多羥基取代之芳族化合物與氟磺化劑反應形成多(氟磺酸酯)取代之芳族化合物;以及(b)使多(氟磺酸酯)取代之芳族化合物與炔烴在催化劑存在下在使炔烴與多(氟磺酸酯)取代之芳族化合物有效偶合的條件下反應且形成多炔基取代之芳烴化合物;其中催化劑包括一個或多個第10族原子或銅錯合物。適用於本發明之芳族化合物在芳基部分上具有兩個或更多個羥基取代基,即芳基部分上的兩個或更多個氫經羥基置換。羥基取代基可在芳基部分的同一芳族環上或不同芳族環上。適合芳基部分為任何個別芳族環或任何稠合環系統,或其任何組合。此類稠合環系統可由2個或更多個,較佳地2至8個稠合環構成,其中至少一個稠合環為芳族。較佳的是2個或更多個稠合環為芳族。適合稠合環系統可僅由稠合芳族環構成,或可由一個或多個芳族環與一
個或多個非芳族環稠合構成。適合芳基部分具有6至50個芳族環原子。具有個別(即非稠合)芳族環的示範性芳基部分包含(但不限於)衍生自以下的彼等芳基部分:苯、聯苯、三聯苯、三苯基苯、六苯基苯、吡啶、聯吡啶、嘧啶、噠嗪、吡咯、咪唑、三嗪、三唑、呋喃、噁唑、噻唑以及噻吩。具有稠合芳族環的示範性芳基部分包含(但不限於)衍生自以下的彼等芳基部分:茀、9,9-二苯基茀、9,9-二萘基茀、咔唑、二苯并呋喃、二苯并噻吩、萘、苊烯、聯萘、苯并蒽、蒽、芘、吲哚、異吲哚、聯伸三苯、并四苯、四苯、并五苯、苝、六苯并苯、喹啉、異喹啉、鄰苯二甲酸酐、苯均四酸二酐、苯并咪唑、苯并三唑、苯并呋喃、苯并噻吩、苯并噁唑以及苯并噻唑。較佳的是,芳基部分不為雜芳基。較佳為衍生自以下的芳基部分:苯、聯苯、三聯苯、三苯基苯、六苯基苯、吡啶、聯吡啶、茀、9,9-二苯基茀、9,9-二萘基茀、咔唑、萘、苊烯、聯萘、苯并蒽、蒽、芘、聯伸三苯、并四苯、四苯、并五苯、苝、六苯并苯、鄰苯二甲酸酐以及苯均四酸二酐。除了具有兩個或更多個羥基取代基之外,芳族化合物的芳基部分可視情況具有一個或多個額外取代基。示範性額外取代基包含(但不限於)含有硼的基團、烷基、鹵烷基、鹵素、C1-12烷氧基、C1-12巰基烷基、C6-20芳氧基、二烷基膦基、二-C6-20芳基膦基、二烷基膦醯基、二-C6-20芳基膦醯基、C2-C8烯烴、三-C1-12烷基矽烷基以及溶解度提高部分。較佳地,多羥基取代之芳族化合物亦具有一個或多個溶解度提高部分。示範性溶解度提高部分包含(但不限於)羥基、羥基烷基(具有1至12個碳原子)、硫代烷基(具有1至12個碳原子)、
巰基烷基(具有1至12個碳原子)、羧酸、羧酸酯(具有2至30個碳原子)、胺(具有0至60個碳原子)、醯胺(具有1至60個碳原子)、銨鹽(具有0至30個碳原子)、硝基、硫醇、磺醯胺(具有0至30個碳原子)、氰基、磺酸以及磺醯基酯(具有1至30個碳原子)。
其中Ar表示具有6至50個芳族環原子的芳基部分;各R1為溶解度提高部分;a為整數2至6;且b為整數0至4。較佳地,Ar選自苯、聯苯、三聯苯、三苯基苯、六苯基苯、吡啶、聯吡啶、嘧啶、噠嗪、吡咯、咪唑、三嗪、三唑、呋喃、噁唑、噻唑、噻吩、茀、9,9-二苯基茀、9,9-二萘基茀、咔唑、二苯并呋喃、二苯并噻吩、萘、苊烯、聯萘、苯并蒽、蒽、芘、吲哚、異吲哚、聯伸三苯、并四苯、四苯、并五苯、苝、六苯并苯、喹啉、異喹啉、鄰苯二甲酸酐、苯均四酸二酐、苯并咪唑、苯并三唑、苯并呋喃、苯并噻吩、苯并噁唑以及苯并噻唑。較佳的是,Ar選自苯、聯苯、三聯苯、三苯基苯、六苯基苯、吡啶、聯吡啶、茀、9,9-二苯基茀、9,9-二萘基茀、咔唑、萘、苊烯、聯萘、苯并蒽、蒽、芘、聯伸三苯、并四苯、四苯、并五苯、苝、六苯并苯、鄰苯二甲酸酐以及苯均四酸二酐。R1的較佳溶解度提高部分包含(但不限於)獨立地選自-OH、C1-12羥基烷基、-C(=O)OR3、
-C(=O)N(R4)2、-O-C(=O)R5、-NR4C(=O)R6、-NO2、-S(=O)2-OR7、-O-S(=O)2-R8、-NR4-S(=O)2-R6、S(=O)2-N(R4)2以及-Si(Z)3;其中R3=H、C1-12烷基、C1-12羥基烷基、C1-12胺基烷基或C6-30芳基;各R4獨立地為H、C6-30芳基或C1-12烷基;各R5獨立地選自H、C1-12烷基、C1-12羥基烷基、C6-30芳基、-O(C1-12烷基)、-O(C6-30芳基)以及-N(R4)2;R6=H、C1-12烷基、C1-12羥基烷基、C6-30芳基、-O(C1-12烷基)或-NH(C1-12烷基);R7=H、C1-12烷基或C6-30芳基;R8=C6-30芳基、C1-12烷基以及鹵基C1-12烷基;各Z獨立地選自C1-12烷基、C1-12羥基烷基、C1-12烷氧基、C1-12烷烴羧酸酯、-N(R4)2或-OSi(Y)3;且各Y選自C1-12烷基、C1-12羥基烷基、C1-12烷氧基或C1-12烷烴羧酸酯。較佳的是,各R1獨立地選自-OH、C1-4羥基烷基、-C(=O)OR3、-C(=O)N(R4)2、-O-C(=O)R5、--S(=O)2-OR6、S(=O)2-N(R4)2以及-Si(Z)3,更佳地選自-OH、C1-4羥基烷基、-C(=O)OR3以及-C(=O)N(R4)2,且更佳地-OH及-C(=O)OR3。優選地,R3為H、C1-6烷基、C1-6羥基烷基、C1-6胺基烷基或C6-30芳基,更佳地H、C1-4烷基或C1-6羥基烷基,且甚至更佳地H。R4優選為H、C6-30芳基或C1-6烷基,且更佳H或C1-4烷基。優選的是,R5為C1-6烷基、C1-6羥基烷基、C6-30芳基、-O(C1-10烷基)或-N(R4)2,且更佳地C1-6烷基、C1-6羥基烷基、C6-20芳基、-O(C1-6烷基)或-N(R4)2。R6優選為H、C1-10烷基、C1-6羥基烷基、C6-20芳基、-O(C1-10烷基)或-N(R4)2,且更佳為H、C1-6烷基、-O(C1-6烷基)或-N(R4)2。R7優選為H、C1-6烷基或C6-20芳基,更佳為H或C1-4烷基,且甚至更佳為H。優選的是,R8為C6-26芳基、C1-10烷基以及
C1-10氟烷基,且更佳為苯基、甲苯基、甲基以及三氟甲基。優選地,a=2至4,且更佳地2至3。優選的是,b=1至3,且更佳地b=1或2。更佳地,a=2至4且b=1至3,且更佳地a=2至3且b=1至3。熟習此項技術者顯而易知,R1中的任何反應性官能團(諸如羥基及羧酸)可經保護。此類羥基及羧酸保護基為熟習此項技術者熟知。適合多羥基取代之芳族化合物市場有售,諸如來自西格瑪-阿爾德里奇(Sigma-Aldrich),或可藉由此項技術中已知的程序製備。
多羥基取代之芳族化合物與氟磺化劑反應形成多(氟磺酸酯)取代之芳族化合物。可使用任何適合氟磺化劑,且較佳為磺醯氟(SO2F2)。較佳地,多羥基取代之芳族化合物與氟磺化劑在鹼存在下在適合溶劑中反應。視情況而言,相轉移催化劑與所述鹼組合使用。在另一視情況存在的實施例中,鹼在水存在下使用。在另一情形中,鹼在有機溶劑存在下使用。在另一情形中,鹼在相轉移催化劑、水或有機溶劑中的一個或多個存在下使用。視情況而言,反應混合物中使用界面活性劑。通常,多羥基取代之芳族化合物與視情況存在的鹼在適合溶劑中組合,隨後添加氟磺化劑。當磺醯氟用作氟磺化劑時,其較佳地以氣體形式使用,但其可替代地在足夠低溫度下使用,使得磺醯氟呈液體狀態。
儘管可使用與氟磺化劑相容的任何適合鹼,但較佳的是,選擇亦與隨後炔烴偶合步驟中所用的催化劑相容的鹼。較佳鹼包含(但不限於)碳酸鹽、磷酸鹽、乙酸鹽及羧酸鹽。無機鹼可適合地用於反應混合物中。碳酸鹽的實例包含(但不限於)碳酸鋰、碳酸鈉、碳酸鉀、碳酸銣、碳酸銫、
碳酸銨、經取代之碳酸銨以及相應碳酸氫鹽。磷酸鹽的實例包含(但不限於)磷酸鋰、磷酸鈉、磷酸鉀、磷酸銣、磷酸銫、磷酸銨、經取代之磷酸銨以及前述的相應磷酸氫鹽。乙酸鹽的實例包含(但不限於)乙酸鋰、乙酸鈉、乙酸鉀、乙酸銣、乙酸銫、乙酸銨以及經取代之乙酸銨。
用於氟磺化步驟的其他適合鹼包含(但不限於)甲酸根、氟乙酸根以及丙酸根負離子與鋰、鈉、鉀、銣、銫、銨以及經取代之銨陽離子的鹽;雙(矽烷基)胺基化合物鹽,諸如雙(三甲基矽烷基)胺基化合物的鋰、鈉及鉀鹽;醇鹽,諸如第三丁醇鹽的鋰、鈉及鉀鹽;金屬氟化物,諸如氟化鈉、氟化鉀、氟化銫、氟化銀、氟化四丁銨、氟化銨以及氟化三乙基銨;金屬氫氧化物;以及非親核有機胺,諸如受阻胺及雜芳烴。本文所用的術語「金屬氫氧化物」包含金屬多氫氧化物,諸如金屬二氫氧化物及金屬三氫氧化物。示範性金屬氫氧化物包含(但不限於)氫氧化鋰、氫氧化鈉、氫氧化鉀、二氫氧化鎂、二氫氧化鈣、二氫氧化鍶、二氫氧化鋇、三氫氧化鋁、三氫氧化鎵、三氫氧化銦以及三氫氧化鉈。示範性非親核有機胺包含(但不限於)三乙胺、吡啶、嗎啉、2,6-二甲基吡啶、N,N-二環己基甲基胺、二異丙基胺、N,N-二異丙基乙胺、1,4-二氮雜雙環[2.2.2]辛烷(DABCO)、1,5-二氮雜二環[4.3.0]壬-5-烯(DBN)、1,8-二氮雜雙環[5.4.0]十一-7-烯(DBU)以及1,8-雙(二甲胺基)萘。
較佳地,每當量的氟磺酸酯存在至少一當量鹼。在一些實施例中,每當量的氟磺酸酯存在不超過10當量鹼。在一些實施例中,每當量的氟磺酸酯存在至少2當量鹼。在
一些實施例中,每當量的氟磺酸酯存在不超過6當量鹼。
選擇氟磺化反應混合物中的溶劑使得其適於與反應物、鹼一起使用,且亦較佳適於與炔烴偶合步驟中所用的反應物、催化劑以及配位體一起使用。舉例而言,適合溶劑包含甲苯、二甲苯(鄰二甲苯、間二甲苯、對二甲苯或其混合物)、苯、水、甲醇、乙醇、1-丙醇、2-丙醇、正丁醇、2-丁醇、戊醇、己醇、第三丁醇、第三戊醇、乙二醇、1,2-丙二醇、1,3-丙二醇、丙三醇、N-甲基-2-吡咯啶酮、乙腈、N,N-二甲基甲醯胺、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸異丙酯、三乙酸甘油酯、丙酮、甲基乙基酮,以及醚溶劑,諸如1,4-二噁烷、四氫呋喃、2-甲基四氫呋喃、乙醚、環戊基甲醚、2-丁基乙基醚、二甲氧基乙烷、聚乙二醇。可適合地採用溶劑的混合物。
視情況而言,氟磺化步驟反應混合物中可包含水。使用氟磺酸酯與三氟甲磺酸酯相比的一個益處在於可進行反應,而無隨後分離步驟,或具有單個分離步驟。在涉及三氟甲磺酸酯的偶合中,需要指定純化步驟來移除副產物,因為產物及副產物通常佔據同一相。在本文所述的反應流程中,副產物在氣相中且將自發地或使用單個脫氣步驟噴湧,或將分配至容易分離的水相中。因此,本文所述的反應流程與涉及三氟甲磺酸酯的偶合相比提供額外益處。
在與氟磺化劑反應之後,獲得多(氟磺酸酯)取代之芳族化合物。氟磺酸酯取代基(或基團)係指具有式-OS(=O)2F的-O-氟磺酸酯。不受理論束縛,咸信氟磺酸酯基團的硫原子鍵結於多羥基取代之芳族化合物的羥基的氧。多
羥基取代之芳族化合物的至少兩個羥基取代基轉化為氟磺酸酯取代基。所用的氟磺化劑的量足以將芳族化合物的芳基部分上的至少兩個羥基取代基轉化成兩個氟磺酸酯取代基。若多羥基取代之芳族化合物在芳基部分上具有超過兩個羥基取代基,則氟磺化劑的量可從足以將兩個羥基取代基轉化成氟磺酸酯取代基的量至足以將全部羥基取代基轉化成氟磺酸酯取代基的量變化。每個打算氟磺化的羥基取代基所用的氟磺化劑的量通常大於或等於1當量。因此,多(氟磺酸酯)取代之芳族化合物中所要的氟磺酸酯取代基的數目取決於打算與芳族化合物偶合的炔烴部分的所要數目。氟磺酸酯取代基可在芳基部分的同一芳族環上或不同芳族環上。
舉例而言,反應流程1說明藉由使式(1)的多羥基取代之芳族化合物與氟磺化劑(FSA)反應形成式(2)的多(氟磺酸酯)取代之芳族化合物的通用反應,其中化合物(1)及(2)中的Ar、R1、a以及b如上文針對化合物(1)所定義;c係指氟磺酸酯取代基的數目且為整數2至6;且d表示任何剩餘羥基取代基且為整數0至4。熟習此項技術者應瞭解,反應流程1中d=a-c。
在隨後步驟中,多(氟磺酸酯)取代之芳族化合物與炔烴在催化劑存在下在使炔烴與多(氟磺酸酯)取代之芳族
化合物有效偶合的條件下反應且形成所要多炔基取代之芳烴化合物。催化劑包括一個或多個第10族原子或銅錯合物。視情況而言,向催化劑的添加中亦可存在一種或多種配位體、一種或多種鹼或一種或多種配位體與一種或多種鹼的組合。此炔烴偶合反應通常在溶劑中進行,且上文針對氟磺化步驟所述的任何溶劑適於炔烴偶合反應。在此炔烴偶合反應中,氟磺酸酯基團用作芳族化合物的離去基團。亦即,在偶合反應期間,芳族化合物中的氟磺酸酯取代基置換成炔烴部分。偶合反應的結果為在芳族化合物與炔烴之間形成新碳-碳鍵。一般而言,此炔烴偶合步驟由反應流程2說明,其中A表示芳族部分且R-C≡C-H表示炔烴。
偶合步驟中可使用多種炔烴來形成本發明之多炔基取代之芳烴。此類炔烴為末端炔烴,即其具有至少一個碳-碳參鍵,其中形成碳-碳參鍵的一個碳鍵結於氫。適合炔烴亦可具有內部碳-碳參鍵鍵聯及/或碳-碳雙鍵鍵聯。適合炔烴亦可含有一個或多個雜原子,諸如氮、氧或硫。適用於本發明偶合反應的典型炔烴具有通式R-C≡C-H,其中R為H或具有1至30個碳原子的有機部分。此類有機部分可為芳族或非芳族。較佳地,R為烷基、雜烷基、羥基烷基、C6-30芳基、C6-30芳基取代之烷基、-CO2Ra、-Si(Za)3,或與薗頭偶合相容的任何其他取代基;其中Ra=H、烷基、烯基、炔基、雜烷基、羥基烷基、C6-30芳基或C6-30芳基取代之烷基;且各Za
獨立地選自H、烷基、雜烷基、C6-30芳基、C6-30芳基取代之烷基以及C1-12烷氧基。較佳炔烴為以下彼等炔烴,其中R=C1-10烷基、C1-10雜烷基、C1-10羥基烷基、C6-30芳基、C6-30芳基取代之烷基、-CO2Ra或-Si(Za)3;其中Ra=H、C1-10烷基、C2-10烯基、C2-10炔基、C1-10雜烷基、C1-10羥基烷基、C6-30芳基、C6-30芳基取代之烷基或C1-30烴基部分,其具有一個或多個溶解度提高取代基;且各Za獨立地選自H、烷基、C6-30芳基、C6-30芳基取代之烷基以及C1-12烷氧基。適合溶解度提高取代基包含(但不限於)-OH、C1-12羥基烷基、-C(=O)OR13、-C(=O)N(R14)2、-O-C(=O)R15、-NR14C(=O)R16、-NO2、-S(=O)2-OR17、-O-S(=O)2-R18、-NR14-S(=O)2-R16、S(=O)2-N(R14)2以及-Si(Z1)3;其中R13=H、C1-12烷基、C1-12羥基烷基、C1-12胺基烷基或C6-30芳基;各R14獨立地為H、C6-30芳基或C1-12烷基;各R15獨立地選自H、C1-12烷基、C1-12羥基烷基、C6-30芳基、-O(C1-12烷基)、-O(C6-30芳基)以及-N(R14)2;R16=H、C1-12烷基、C1-12羥基烷基、C6-30芳基、-O(C1-12烷基)或-NH(C1-12烷基);R17=H、C1-12烷基或C6-30芳基;R18=C6-30芳基、C1-12烷基以及鹵基C1-12烷基;各Z1獨立地選自C1-12烷基、C1-12羥基烷基、C1-12烷氧基、C1-12烷烴羧酸酯、-N(R14)2或-OSi(Y1)3;且各Y1選自C1-12烷基、C1-12羥基烷基、C1-12烷氧基或C1-12烷烴羧酸酯。熟習此項技術者應瞭解可使用炔烴混合物。熟習此項技術者亦顯而易知,末端炔烴中的任何反應性官能團(諸如羥基及羧酸)可經保護。此類羥基及羧酸保護基為熟習此項技術者熟知。適合炔烴一般市場有售,諸如來自西格瑪-阿爾德里奇,或可藉
由此項技術中已知的方法製備。
反應流程3說明較佳偶合反應,其中式(2)的多(氟磺酸酯)取代之芳族化合物與炔烴(R-C≡C-H)在催化劑存在下反應,獲得式(3)的多炔烴取代之芳烴,其中Ar、R1、R、a、b、c以及d如上文所述。
此處的炔烴偶合反應使用一種或多種催化劑,其選自具有至少一個第10族原子或銅錯合物的催化劑。可使用催化劑混合物,諸如具有至少一個第10族原子及銅錯合物的催化劑的混合物。視情況而言,除了催化劑之外,炔烴偶合反應可包含配位體及鹼。第10族原子包含鎳、鈀及鉑。催化劑以適於反應條件的形式提供。舉例而言,催化劑可提供於基板上,或具有至少一個第10族原子的催化劑可由一種或多種前催化劑及一種或多種配位體原位產生。在一種情形中,使用基於鎳的催化劑。在另一情形中,使用基於鉑的催化劑。在另一情形中,使用包含基於鎳、鉑及鈀的催化劑中的一個或多個的催化劑。
鈀預催化劑的實例包含(但不限於)乙酸鈀(II)、氯化鈀(II)、二氯雙(乙腈)鈀(II)、二氯雙(苯甲腈)鈀(II)、氯化烯丙基鈀二聚體、乙醯基丙酮酸鈀(II)、溴化鈀(II)、雙(二苯亞甲基丙酮)鈀(0)、氯化雙(2-甲基烯丙基)鈀二聚體、氯化巴
豆基鈀二聚體、二氯(1,5-環辛二烯)鈀(II)、二氯(降冰片二烯)鈀(II)、三氟乙酸鈀(II)、苯甲酸鈀(II)、三甲基乙酸鈀(II)、氧化鈀(II)、氰化鈀(II)、參(二苯亞甲基丙酮)二鈀(0)、六氟乙醯基丙酮鈀(II)、順-二氯(N,N,N',N'-四甲基乙二胺)鈀(II)以及環戊二烯基[(1,2,3-n)-1-苯基-2-丙烯基]鈀(II)。在一種情形中,使用吡啶加強型預催化劑製備、穩定及起始(PEPPSI)型催化劑,例如二氯化[1,3-雙(2,6-二異丙基苯基)亞咪唑-2-基](3-氯吡啶基)鈀(II)及二氯化(1,3-雙(2,6-二異丙基苯基)亞咪唑基)(3-氯吡啶基)鈀(II)。
鎳預催化劑的實例包含(但不限於)乙酸鎳(II);氯化鎳(II);二氯化雙(三苯膦)鎳(II);二氯化雙(三環己基膦)鎳(II);[1,1'-雙(二苯膦基)二茂鐵]二氯鎳(II);二氯[1,2-雙(二乙基膦基)乙烷]鎳(II);氯(1-萘基)雙(三苯膦)鎳(II);氯化1,3-雙(2,6-二異丙基苯基)咪唑鎓;雙(1,5-環辛二烯)鎳(0);氯化鎳(II)乙二醇二甲醚複合物;[1,3-雙(二苯膦基)丙烷]二氯鎳(II);[1,2-雙(二苯膦基)乙烷]二氯鎳(II);以及雙(三環己基膦)鎳(0)。
較佳地選擇炔烴偶合反應混合物中所用的配位體從前催化劑產生所選催化劑。舉例而言,配位體可為膦配位體、碳烯配位體、基於胺的配位體、基於羧酸酯的配位體、胺基葡聚糖、基於胺基膦的配位體或基於N-雜環碳烯的配位體。在一種情形中,配位體為單齒的。在另一情形中,配位體為雙齒的。在另一情形中,配位體為多齒的。
適合膦配位體可包含(但不限於)含有官能化芳基或烷基取代基的單齒及雙齒膦或其鹽。舉例而言,適合膦
配位體包含(但不限於)三苯膦;三(鄰甲苯基)膦;參(4-甲氧基苯基)膦;參(五氟苯基)膦;三(對甲苯基)膦;三(2-呋喃基)膦;參(4-氯苯基)膦;二(1-金剛烷基)(1-萘甲醯基)膦;苯甲基二苯基膦;1,1'-雙(二-第三丁基膦基)二茂鐵;(-)-1,2-雙((2R,5R)-2,5-二甲基磷雜環戊烷基)苯;(-)-2,3-雙[(2R,5R)-2,5-二甲基磷雜環戊烷基]-1-[3,5-雙(三氟甲基)苯基]-1H-吡咯-2,5-二酮;1,2-雙(二苯膦基)苯;2,2'-雙(二苯膦基)-1,1'-聯萘;2,2'-雙(二苯膦基)-1,1'-聯苯、1,4-雙(二苯膦基)丁烷;1,2-雙(二苯膦基)乙烷;2-[雙(二苯膦基)甲基]吡啶;1,5-雙(二苯膦基)戊烷;1,3-雙(二苯膦基)丙烷;1,1'-雙(二-異丙基膦基)二茂鐵;(S)-(-)-5,5'-雙[二(3,5-二甲苯基)膦基]-4,4'-聯-1,3-苯并間二氧雜環戊烯;三環己基膦(本文稱為PCy3);四氟硼酸三環己基膦(本文稱為PCy3‧HBF4);N-[2-(二-1-金剛烷基膦基)苯基]嗎啉;2-(二-第三丁基膦基)聯苯;2-(二-第三丁基膦基)-3,6-二甲氧基-2',4',6'-三-異丙基-1,1'-聯苯;2-二-第三丁基膦基-2'-(N,N-二甲基胺基)聯苯;2-二-第三丁基膦基-2'-甲基聯苯;二環己基苯基膦;2-(二環己基膦基)-3,6-二甲氧基-2',4',6'-三-異丙基-1;2-(二環己基膦基)-2'-(N,N-二甲基胺基)聯苯;2-二環己基膦基-2',6'-二甲基胺基-1,1'-聯苯;2-二環己基膦基-2',6'-二-異丙氧基-1,1'-聯苯;2-二環己基膦基-2'-甲基聯苯;2-[2-(二環己基膦基)苯基]-1-甲基-1H-吲哚;2-(二環己基膦基)-2',4',6'-三-異丙基-1,1'-聯苯;[4-(N,N-二甲基胺基)苯基]二-第三丁基膦;9,9-二甲基-4,5-雙(二苯基膦基)氧雜蒽;(R)-(-)-1-[(S)-2-(二苯基膦基)二茂鐵]乙基二環己基膦;三苯甲基膦;三-第三丁基膦;三-正丁基膦;以及1,1'-雙(二苯基
膦基)二茂鐵。
適合基於胺及胺基膦的配位體包含單齒或雙齒烷基及芳族胺的任何組合,包含(但不限於):吡啶;2,2'-聯吡啶;4,4'-二甲基-2,2'-聯吡啶;1,10-啡啉;3,4,7,8-四甲基-1,10-啡啉;4,7-二甲氧基-1,10-啡啉;N,N,N',N'-四甲基乙二胺;1,3-二胺基丙烷;氨;4-(胺基甲基)吡啶;(1R,2S,9S)-(+)-11-甲基-7,11-二氮雜三環[7.3.1.02,7]十三烷;2,6-二-第三丁基吡啶;2,2'-雙[(4S)-4-苯甲基-2-噁唑啉];2,2-雙((4S)-(-)-4-異丙基噁唑啉)丙烷;2,2'-亞甲基雙[(4S)-4-苯基-2-噁唑啉];以及4,4'-二-第三丁基-2,2'聯吡啶。另外,胺基膦配位體諸如2-(二苯膦基)乙胺、2-(2-(二苯膦基)乙基)吡啶、(1R,2R)-2-(二苯膦基)環己胺以及2-(二-第三丁基膦基)乙胺。
適合碳烯配位體包含基於N-雜環碳烯(NHC)的配位體,包含(但不限於):氯化1,3-雙(2,4,6-三甲基苯基)咪唑啉鎓;氯化1,3-雙(2,6-二異丙基苯基)咪唑鎓;氯化1,3-雙-(2,6-二異丙基苯基)咪唑啉鎓;氯化1,3-二異丙基咪唑鎓以及氯化1,3-二環己基苯并咪唑鎓。
視情況而言,除了第10族催化劑之外,本發明反應中可使用助催化劑。在一種情形中,助催化劑為已知用於薗頭偶合中的銅錯合物。在一種情形中,銅錯合物為銅(I)的鹵化物鹽,例如碘化銅或氯化銅。不受理論限制,可使用第10族催化劑及銅催化劑來提高反應速率。或者,可在使用或不使用第10族催化劑的情況下使用銅錯合物作為催化劑。
可藉由進行離散步驟或藉由進行一鍋式反應根據本發明製備本發明多炔基取代之芳烴。當以離散步驟進行
時,第一步驟包括使多羥基取代之芳族化合物與氟磺化劑在鹼存在下反應,提供多(氟磺酸酯)取代之芳族化合物,且第二步驟包括在催化劑存在下偶合多(氟磺酸酯)取代之芳族化合物與炔烴。粗聚氟磺化產物無需分離,而是可直接在單個鍋中進行催化的薗頭交叉偶合。因此,本發明方法可作為一鍋式反應進行,多羥基取代之芳族化合物首先與氟磺化劑在鹼存在下反應,且接著與炔烴在催化劑存在下反應。
可根據本發明製備的示範性多炔基取代之芳烴包含(但不限於)以下結構,其中各R如上文所定義且各R9獨立地選自H及R1,其中各R1如上文所定義。
實例1.向500mL 3頸圓底燒瓶中添加間苯三酚(10.0g;79.3mmol)及碳酸鉀(36.3g;238mmol),所述燒瓶排放至氣液分離罐(knockout pot)及鹼洗氣器。向混合物中添加120mL二甲基甲醯胺(DMF)。磺醯氟表面下緩慢鼓泡進入反應混合物。反應混合物用氮氣淨化且斷開連接氣液分離罐,且換成氮氣鼓泡器。經注射器添加向反應混合物中添加2-甲基-3-丁炔-2-醇(19.2mL;208mmol)及三乙胺(33.1mL;236mmol)。在手套箱中預先稱重環戊二烯基[(1,2,3-n)-1-苯基-2-丙烯基]鈀(II)(「CpPd(苯烯丙基)」)(0.227g;0.79mmol)、三苯膦(0.625g;2.36mmol)及碘化銅(I)(0.605g)且在微正壓氮氣壓力下將混合物添加至反應燒瓶中。將反應混合物加熱至50℃且在此溫度下攪拌直至藉由液相層析-質譜(LCMS)分析混合物顯示形成所要產物。粗反應混合物用稀HCl洗滌且萃取至1L乙酸乙酯中。藉由在60℃下旋轉蒸發移除揮發物。粗物質用2N氫氧化鈉水溶液(400mL)及MTBE(400mL)處理且將所得兩相混合物轉移至分液漏斗。振盪及分離各層。水層經水潤濕矽藻土床過濾且濾餅用400mL水洗滌。在劇烈攪拌下,濾液用12.1N鹽酸處理直至獲得pH<1。將水相轉移至2L分液漏斗中且用甲基第三丁基醚(MTBE)(2×200mL)萃取。將經合併的有機萃取物蒸發至乾燥。將固體殘基重新溶解於乙醚(約250mL)中且經矽藻土過濾。藉由旋轉蒸發且接著在高度真空(<1mmHg)下在50℃下濃縮濾液且預期提供化合物4。
實例2.向30mL裝配有磁力攪拌棒及螺紋蓋的玻璃閃爍瓶依序裝入來自實例1的化合物4(0.5g,1.93mmol,1.0當量)、粉末狀氫氧化鉀(0.572g,14.32mmol,7.4當量)以及1,4-二噁烷(10.0mL)。將小瓶蓋上蓋子且置於預熱至100℃的鋁塊中,且在此溫度下攪拌反應混合物120分鐘。接著使反應混合物冷卻至室溫,且用10mL 6N鹽酸及75mL MTBE稀釋。振盪及分離各層。藉由直接重力過濾至分液漏斗中來移除存在的固體。振盪及分離各層且有機相用去離子水(1×)及鹽水(1×)依序洗滌。將有機層傾析至配衡圓底燒瓶中,且藉由旋轉蒸發,且接著在高真空(<1mmHg)下濃縮,且預期提供粗化合物5。
實例3.向500mL 3頸圓底燒瓶中添加3,5-二羥基苯甲酸(10.0g;83.9mmol)及碳酸鉀(38.4g;252mmol),所述燒瓶排放至氣液分離罐及鹼洗氣器。向混合物中添加125mL二甲基甲醯胺(DMF)。磺醯氟表面下緩慢鼓泡進入反應混合物。6小時後,藉由液相層析-質譜(LCMS)分析顯示將起始物質轉換成所要雙-氟磺酸酯。反應混合物用氮氣淨化且斷開連接氣液分離罐,且換成氮氣鼓泡器。經注射器添加向反應混合物添加2-甲基-3-丁炔-2-醇(20.3mL;220mmol)
及三乙胺(35mL;250mmol)。在手套箱中預先稱重CpPd(苯烯丙基)(0.240g;0.84mmol)、三苯膦(0.661g;2.52mmol)以及碘化銅(I)(0.640g)且在微正壓氮氣壓力下將混合物添加至反應燒瓶中。反應混合物變成暗黑色。將反應混合物加熱至50℃隔夜(15小時)。LCMS分析顯示形成約2:1比率的所要產物及單取代中間物。額外加熱6小時後,未觀測至產物比率的改變。向混合物中添加在手套箱中預先稱重的額外催化劑前驅體CpPd(苯烯丙基)(0.121g)、三苯膦(0.330g)以及碘化銅(I)(0.320g)。在50℃下攪拌反應混合物隔夜。LCMS顯示形成所要產物。粗反應混合物用稀HCl洗滌且萃取至1L乙酸乙酯中。藉由在60℃下旋轉蒸發移除揮發物,展現黑色淤渣。藉由1H NMR光譜法分析所得材料顯示所要產物及DMF。粗物質用2N氫氧化鈉水溶液(400mL)及MTBE(400mL)處理且將所得兩相混合物轉移至2L分液漏斗中。振盪及分離各層。水層經水濕潤矽藻土床過濾且濾餅用約400mL水洗滌。在劇烈攪拌下,濾液用12.1N鹽酸處理直至獲得pH<1。pH擺動誘導形成渾濁/固體。非均質水相轉移至2L分液漏斗且用甲基第三丁基醚(MTBE)(2×200mL)萃取。經合併的有機萃取物蒸發至乾燥以提供深褐色油性泡沫。此物質的1H NMR光譜收集於THF-d8中。將固體殘餘物重新溶解於乙醚(約250mL)中且經矽藻土過濾。藉由旋轉蒸發,接著在高度真空(<1mmHg)下在50℃下濃縮提供呈深褐色油性泡沫狀的化合物6(14.3g;59%)。藉由1H及13C NMR光譜法確認化合物。
實例4:向30mL裝配有磁力攪拌棒及螺紋蓋的玻璃閃爍瓶依序裝入來自實例3的化合物6(0.493g,0.84mmol,1.0當量,49重量%純度)、粉末狀氫氧化鉀(0.399g,6.26mmol,7.4當量)以及1,4-二噁烷(5.0mL)。將小瓶蓋上蓋子且置於預熱至100℃的鋁塊中,且在此溫度下攪拌反應混合物60分鐘。接著使反應混合物略微冷卻,接著收集約0.1mL樣品。樣品用6N鹽酸及MTBE稀釋。振盪及分離各層。移除且丟棄水(底部)層。藉由旋轉蒸發來濃縮有機層。深褐色油性殘餘物溶解於THF-d8中且藉由1H NMR光譜法分析。反應混合物重新加熱至100℃。再攪拌60分鐘後,冷卻反應混合物且取樣。如上文所述對樣品進行處理及分析。反應混合物用6N鹽酸(約35mL)及MTBE稀釋。藉由直接重力過濾至分液漏斗中將存在的大部分不溶性深褐色固體物質移除。振盪及分離各層且有機相用去離子水(1×)及鹽水(1×)依序洗滌。有機層傾析至配衡圓底燒瓶中且藉由旋轉蒸發,且接著在高度真空(<1mmHg)下濃縮,留下呈橙色固體殘餘物的粗3,5-二乙炔基苯甲酸(化合物7)(0.223g)。粗物質的樣品(27.6mg)與1,4-雙(三甲基矽烷基)苯(31.5mg,0.1412mmol,99.7重量%純度)組合且將混合物溶解於THF-d8(0.75mL)中。所得溶液藉由0.2μm尼龍針筒過濾器且藉由1H NMR光譜法(16次掃描,20秒弛豫延遲)分析濾液。基
於針對1,4-雙(三甲基矽烷基)苯調諧的相對整合,測得化合物7的純度為28重量%,此對應於43%產率。藉由1H及13C NMR光譜法確認化合物的結構。
實例5.向500mL 3頸圓底燒瓶中添加二羥基異苯并呋喃二酮(10.0g;55.5mmol)及碳酸鉀(25.4g;167mmol),所述燒瓶排放至氣液分離罐及鹼洗氣器。向混合物中添加90mL二甲基甲醯胺(DMF)。磺醯氟表面下緩慢鼓泡進入反應混合物。反應混合物用氮氣淨化且斷開連接氣液分離罐,且換成氮氣鼓泡器。經注射器添加向反應混合物中添加2-甲基-3-丁炔-2-醇(13.4mL;146mmol)及三乙胺(23.2mL;165mmol)。在手套箱中預先稱重CpPd(苯烯丙基)(0.159g;0.55mmol)、三苯膦(0.438g;1.65mmol)以及碘化銅(I)(0.423g)且在微正壓氮氣壓力下將混合物添加至反應燒瓶中。將反應混合物加熱至50℃且在此溫度下攪拌直至LCMS顯示形成所要產物。粗反應混合物用稀HCl洗滌且萃取至1L乙酸乙酯中。藉由在60℃下旋轉蒸發移除揮發物。粗物質用2N氫氧化鈉水溶液(325mL)及MTBE(325mL)處理且將所得兩相混合物轉移至分液漏斗。振盪及分離各層。水層經水潤濕矽藻土床過濾且濾餅用400mL水洗滌。在劇烈攪拌下,濾液用12.1N鹽酸處理直至獲得pH<1。將水相轉移至2L分液漏斗中且用甲基第三丁基醚(MTBE)(2×150mL)萃取。將經合併的有機萃取物蒸發至乾燥。將固體殘基重新溶解於
乙醚(約200mL)中且經矽藻土過濾。藉由旋轉蒸發,且接著在高度真空(<1mmHg)下在50℃下濃縮濾液且預期提供化合物8。
實例6:向30mL裝配有磁力攪拌棒及螺紋蓋的玻璃閃爍瓶依序裝入來自實例5的化合物8(0.5g,1.60mmol,1.0當量)、粉末狀氫氧化鉀(0.474g,11.85mmol,7.4當量)以及1,4-二噁烷(10.0mL)。將小瓶蓋上蓋子且置於預熱至100℃的鋁塊中,且在此溫度下攪拌反應混合物120分鐘。接著使反應混合物冷卻至室溫,且用10mL 6N鹽酸及75mL MTBE稀釋。振盪及分離各層。使用重力過濾至分液漏斗中移除存在的任何固體。振盪及分離各層且有機相用去離子水(1×)及鹽水(1×)依序洗滌。將有機層傾析至配衡圓底燒瓶中,且藉由旋轉蒸發,且接著在高真空(<1mmHg)下濃縮,且預期提供粗化合物9。
實例7.使用表1中的多羥基取代之芳族化合物及表2中的炔烴重複實例3的通用程序製備表3中的多炔基取
代之芳烴化合物。在表3中,氟磺化劑(FSA)的莫耳數指示轉化成炔基取代基的羥基取代基的數目。
實例8.向裝備有頂置式攪拌器(PTFE槳式攪拌器)、PTFE塗佈熱電偶、磺醯氟(SO2F2)入口管線及格雷安冷凝器(裝配有排放至氫氧化鈉水溶液(1N)洗氣器的頂部空間出口管線)的3-頸2-L圓底燒瓶裝入3,5-二羥基苯甲酸甲酯(30.17g,174mmol,1.0當量)、粉末狀碳酸鉀(60.42g,433mmol,2.5當量)及450mL乙酸乙酯(EtOAc)。開始頂置式攪拌且將氣態SO2F2表面下鼓入反應混合物中持續幾個小時。反應達到完全轉化(如藉由1H NMR光譜法對過濾濃縮反應器樣品的分析所證明)後,SO2F2入口管線置換成氮氣入口管線且淨化系統幾分鐘。藉由經置於中等孔隙率玻璃粉外殼上的1μm Whatman GFB玻璃微光纖介質真空過濾移除無機鹽且用新鮮EtOAc洗滌鹽濾餅。有機濾液藉由旋轉蒸發,且接著在高度真空(<1mmHg)下隔夜來濃縮,獲得呈淺黃色油狀的3,5-雙[(氟磺醯基)氧基]苯甲酸甲酯(57.62g,173mmol,定量產率)。油狀物在轉移至琥珀色玻璃儲存
瓶中時容易結晶。藉由1H及13C NMR光譜法確認產物3,5-雙[(氟磺醯基)氧基]苯甲酸甲酯。
實例9.向裝配有PTFE塗佈磁力攪拌棒的250-mL 3頸圓底燒瓶裝入來自實例8的3,5-雙[(氟磺醯基)氧基]苯甲酸甲酯(5.00g,15.06mmol,1.0當量)且將燒瓶轉移至氮氣填充的手套箱中。在氮氣填充的手套箱中,向10-mL玻璃閃爍瓶裝入三苯膦(0.245g,0.92mmol,6莫耳%)、乙酸鈀(II)(0.097g,0.43mmol,3莫耳%)及碘化銅(I)(0.170g,0.89mmol,6莫耳%)。向含有3,5-雙[(氟磺醯基)氧基]苯甲酸甲酯的圓底燒瓶中添加50mL無水二甲基甲醯胺(DMF),且在磁力攪拌下添加前催化劑混合物,產生深棕褐色均質溶液。接著依序添加(三甲基矽烷基)乙炔(5.5mL,37.86mmol,2.5當量)及無水三乙胺(5.3mL,37.84mL,2.5當量)。(三甲基矽烷基)乙炔的添加伴隨反應混合物顏色從深棕褐色變成幾乎黑色。反應燒瓶用橡膠隔膜密封,從手套箱移動至通風櫥,且裝配戴氏冷凝器(Dimroth condenser),氮氣入口及PTFE塗佈的熱電偶。此時,顯而易見添加三乙胺會誘發放熱。放熱達到峰值(約45℃)時,反應燒瓶裝配加熱套且使反應混合物升溫至50℃,且在此溫度下攪拌隔夜。攪拌15小時後,藉由GC/MS分析反應混合物揭示起始物質已消耗完且乾淨地形成所要產物。將反應混合物轉移至單頸圓底燒瓶且藉由旋轉蒸發來濃縮(60℃下約10mmHg)。所得深褐色漿液分配於MTBE(250mL)及1N鹽酸(100mL)之間,此誘導形成乳液。兩相混合物經水濕潤Celite®床過濾且接著分離各層。剩餘的破碎層與水層一起。有機層用1N鹽酸(100mL)洗滌。
用MTBE(2×50mL)萃取經合併的水性洗滌液。經合併的有機萃取物用半飽及鹽水(100mL)、鹽水(1×)洗滌,乾燥(無水Na2SO4),過濾且藉由旋轉蒸發來濃縮。將所得深褐色粗殘餘物溶解於最小量的2% EtOAc/己烷中且藉由根據完全溶離所要產物使用額外2% EtOAc/己烷的矽膠床(約25g)塞過濾。藉由旋轉蒸發來濃縮濾液,接著在高度真空(<1mmHg)下濃縮隔夜獲得呈高度黏稠橙色油狀的3,5-雙[(三甲基矽烷基)乙炔基]苯甲酸甲酯(4.61g,14.03mmol,93%產率)。油狀物在環境溫度下靜置時結晶。藉由1H及13C NMR光譜法確認產物3,5-雙[(三甲基矽烷基)乙炔基]苯甲酸甲酯。
實例10.向裝配有頂置式攪拌器(PTFE槳式攪拌器)、氮氣入口、戴氏冷凝器、125mL均壓加料漏斗及PFTE塗佈的熱電偶的1-L4頸圓底燒瓶裝入3,5-雙[(三甲基矽烷基)乙炔基]苯甲酸甲酯(24.37g,74.17mmol,1.0當量)及甲醇(300mL)。反應器用橡膠隔膜密封且開始攪拌。需要用空氣加熱槍溫及加熱至約35℃來完成酯的溶解。同時,單水合氫氧化鋰的樣品(15.60g,372mmol,5.0當量)與HPLC級水(75mL)組合且所得混合物超音波處理幾分鐘以幫助鹼溶解。藉由過濾移除氫氧化鋰溶液中剩餘的任何不溶性材料且將濾液裝入加料漏斗中。接著經5分鐘時程逐滴添加氫氧化鋰水溶液。在此期間,內部溫度從36℃增加至46℃。在環境溫度下攪拌1.5小時後,移除0.1mL反應混合物樣品且用1N HCl/CH3CN(0.5mL/4.0mL)稀釋。藉由LC/MS分析樣品揭示已乾淨地形成所要產物。將反應混合物轉移至單頸圓底燒瓶且藉由旋轉蒸發來濃縮(40℃下約10mmHg)。含水漿料與
HPLC級水(300mL)及MTBE(100mL)組合。振盪及分離各層且有機層作為有害廢物丟棄。將水層轉移至1L愛倫美氏燒瓶(Erlenmeyer flask)中且在劇烈攪拌下,使用6N HCl(81g)將均質溶液酸化至pH約1,此誘導形成深米色漿液。漿液與MTBE(150mL)在分液漏斗中組合且振盪各層產生均質兩相系統。分離各層且用MTBE(2×150mL)萃取水層。經合併的有機萃取物與活化碳(約5g,Darco® G-60,100目)一起攪拌幾分鐘,且接著過濾。藉由旋轉蒸發且接著在真空烘箱(50℃下<1mmHg)中濃縮濾液獲得呈米色固體狀的3,5-二乙炔基苯甲酸(11.56g,65.42mmol,88%產率)。藉由1H及13C NMR光譜法確認產物3,5-二乙炔基苯甲酸。基於使用吡嗪作為內標的定量13C NMR分光鏡分析,測得3,5-二乙炔基苯甲酸的純度為96.3重量%。
Claims (12)
- 一種形成多炔基-芳烴化合物的方法,其包括:(a)使多羥基取代之芳族化合物與氟磺化劑反應形成多(氟磺酸酯)取代之芳族化合物;以及(b)使所述多(氟磺酸酯)取代之芳族化合物與炔烴在催化劑存在下在使所述炔烴與所述多(氟磺酸酯)取代之芳族化合物有效偶合的條件下反應且形成多炔基取代之芳烴化合物;其中所述催化劑包括一個或多個第10族原子或銅錯合物。
- 如申請專利範圍第1項之方法,其中所述反應混合物進一步包括配位體及鹼。
- 如申請專利範圍第2項之方法,其中所述配位體包含以下中的一個或多個:膦配位體、碳烯配位體、基於胺的配位體以及基於胺基膦的配位體。
- 如申請專利範圍第2項之方法,其中所述鹼為碳酸鹽、磷酸鹽、乙酸鹽或羧酸鹽。
- 如申請專利範圍第1項之方法,其中所述芳族化合物具有1至8個芳族環。
- 如申請專利範圍第1項之方法,其中所述芳族化合物具有源自以下的芳基部分:苯、聯苯、三聯苯、三苯基苯、六苯基苯、吡啶、聯吡啶、嘧啶、縫嗪、吡咯、咪唑、三嗪、三唑、呋喃、噁唑、噻唑、噻吩、茀、9,9-二苯基茀、9,9-二萘基茀、咔唑、二苯并呋喃、二苯并噻吩、萘、聯萘、苯并蒽、蒽、芘、吲哚、異吲哚、聯伸三苯、并四苯、四苯、并五苯、苝、六苯并苯、喹啉、異喹啉、鄰苯二甲酸 酐、苯均四酸二酐、苯并咪唑、苯并三唑、苯并呋喃、苯并噻吩、苯并噁唑以及苯并噻唑。
- 如申請專利範圍第1項之方法,其中所述芳族化合物為雜芳族。
- 如申請專利範圍第1項之方法,其中所述芳族化合物具有一個或多個選自以下的取代基:羧酸、羧酸酐、C1-20酯、經取代之C1-20酯、C1-12烷氧基、C1-12烷基、C1-12雜烷基、經取代之C1-12烷基、C2-12烯基、氰基、硝基、羥基、經保護的羥基、鹵基、醯胺基、胺基、巰基、硫離子基、矽烷基、膦基以及膦醯基。
- 如申請專利範圍第1項之方法,其中所述催化劑為鈀催化劑或鎳催化劑或銅錯合物中的一個或多個。
- 如申請專利範圍第1項之方法,其中所述炔烴為一級炔烴。
- 如申請專利範圍第1項之方法,其中所述催化劑包括一個或多個第10族原子及銅錯合物。
- 一種形成多炔基-芳烴化合物的方法,其包括:(a)提供多(氟磺酸酯)取代之芳族化合物;以及(b)使所述多(氟磺酸酯)取代之芳族化合物與炔烴在催化劑存在下在使所述炔烴與所述多(氟磺酸酯)取代之芳族化合物有效偶合的條件下反應且形成多炔基取代之芳烴化合物;其中所述催化劑包括一個或多個第10族原子或銅錯合物。
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