TWI634947B - 用於烷氧基羰基化的苯系雙膦配位子 - Google Patents
用於烷氧基羰基化的苯系雙膦配位子 Download PDFInfo
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- TWI634947B TWI634947B TW105122754A TW105122754A TWI634947B TW I634947 B TWI634947 B TW I634947B TW 105122754 A TW105122754 A TW 105122754A TW 105122754 A TW105122754 A TW 105122754A TW I634947 B TWI634947 B TW I634947B
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- TW
- Taiwan
- Prior art keywords
- alkyl
- heteroaryl
- group
- cycloalkyl
- aryl
- Prior art date
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- 238000007083 alkoxycarbonylation reaction Methods 0.000 title claims abstract description 19
- 239000003446 ligand Substances 0.000 title abstract description 53
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title description 15
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 76
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 87
- 238000000034 method Methods 0.000 claims description 55
- -1 sulphamoyl Chemical group 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 39
- 125000004432 carbon atom Chemical group C* 0.000 claims description 34
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 27
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 claims description 22
- 125000001072 heteroaryl group Chemical group 0.000 claims description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 17
- 150000002148 esters Chemical class 0.000 claims description 17
- 239000005977 Ethylene Substances 0.000 claims description 16
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 11
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 claims description 10
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 claims description 10
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 8
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 8
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 8
- 125000004076 pyridyl group Chemical group 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- 125000002541 furyl group Chemical group 0.000 claims description 5
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 claims description 4
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000002883 imidazolyl group Chemical group 0.000 claims description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 4
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 4
- 125000001544 thienyl group Chemical group 0.000 claims description 4
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 claims description 3
- QMMOXUPEWRXHJS-HWKANZROSA-N (e)-pent-2-ene Chemical compound CC\C=C\C QMMOXUPEWRXHJS-HWKANZROSA-N 0.000 claims description 3
- QMMOXUPEWRXHJS-HYXAFXHYSA-N (z)-pent-2-ene Chemical compound CC\C=C/C QMMOXUPEWRXHJS-HYXAFXHYSA-N 0.000 claims description 3
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 3
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 3
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 claims description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- 125000003838 furazanyl group Chemical group 0.000 claims description 3
- 125000001041 indolyl group Chemical group 0.000 claims description 3
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 claims description 3
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 3
- 125000001786 isothiazolyl group Chemical group 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 125000002971 oxazolyl group Chemical group 0.000 claims description 3
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 3
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 3
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 3
- 125000003831 tetrazolyl group Chemical group 0.000 claims description 3
- 125000000335 thiazolyl group Chemical group 0.000 claims description 3
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 claims description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- RBYGDVHOECIAFC-UHFFFAOYSA-L acetonitrile;palladium(2+);dichloride Chemical compound [Cl-].[Cl-].[Pd+2].CC#N.CC#N RBYGDVHOECIAFC-UHFFFAOYSA-L 0.000 claims description 2
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- RRHPTXZOMDSKRS-PHFPKPIQSA-L (1z,5z)-cycloocta-1,5-diene;dichloropalladium Chemical compound Cl[Pd]Cl.C\1C\C=C/CC\C=C/1 RRHPTXZOMDSKRS-PHFPKPIQSA-L 0.000 claims 1
- JZIBVTUXIVIFGC-UHFFFAOYSA-N 2H-pyrrole Chemical compound C1C=CC=N1 JZIBVTUXIVIFGC-UHFFFAOYSA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 claims 1
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 1
- 125000004093 cyano group Chemical group *C#N 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- 150000003949 imides Chemical class 0.000 claims 1
- 229960004592 isopropanol Drugs 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 125000000101 thioether group Chemical group 0.000 claims 1
- 125000003396 thiol group Chemical group [H]S* 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 description 64
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 44
- 239000000243 solution Substances 0.000 description 43
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 39
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 30
- 150000001336 alkenes Chemical class 0.000 description 27
- 239000000047 product Substances 0.000 description 25
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 22
- 229910052786 argon Inorganic materials 0.000 description 21
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 18
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 18
- 238000004817 gas chromatography Methods 0.000 description 18
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 17
- 239000002253 acid Substances 0.000 description 17
- 238000006063 methoxycarbonylation reaction Methods 0.000 description 16
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 10
- 239000002184 metal Chemical class 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
- 125000006413 ring segment Chemical group 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 125000005842 heteroatom Chemical group 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- IEHIOXQFWRLVGR-UHFFFAOYSA-N methyl 7-methyloctanoate Chemical compound COC(=O)CCCCCC(C)C IEHIOXQFWRLVGR-UHFFFAOYSA-N 0.000 description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 description 4
- 125000006707 (C3-C12) heterocycloalkyl group Chemical group 0.000 description 4
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 4
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 4
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910000085 borane Inorganic materials 0.000 description 4
- ULDHMXUKGWMISQ-UHFFFAOYSA-N carvone Chemical compound CC(=C)C1CC=C(C)C(=O)C1 ULDHMXUKGWMISQ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 235000019439 ethyl acetate Nutrition 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- IUYHWZFSGMZEOG-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].C[CH-]C IUYHWZFSGMZEOG-UHFFFAOYSA-M 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000006384 oligomerization reaction Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 3
- UPSVYNDQEVZTMB-UHFFFAOYSA-N 2-methyl-1,3,5-trinitrobenzene;1,3,5,7-tetranitro-1,3,5,7-tetrazocane Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O.[O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UPSVYNDQEVZTMB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 3
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- FMGGHNGKHRCJLL-UHFFFAOYSA-N 1,2-bis(chloromethyl)benzene Chemical group ClCC1=CC=CC=C1CCl FMGGHNGKHRCJLL-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 2
- 125000000389 2-pyrrolyl group Chemical group [H]N1C([*])=C([H])C([H])=C1[H] 0.000 description 2
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 2
- OWWRMMIWAOBBFK-UHFFFAOYSA-N 3,4-dimethylhex-1-ene Chemical compound CCC(C)C(C)C=C OWWRMMIWAOBBFK-UHFFFAOYSA-N 0.000 description 2
- QDMFTFWKTYXBIW-UHFFFAOYSA-N 3-Methyl-1-heptene Chemical compound CCCCC(C)C=C QDMFTFWKTYXBIW-UHFFFAOYSA-N 0.000 description 2
- MKNQNPYGAQGARI-UHFFFAOYSA-N 4-(bromomethyl)phenol Chemical compound OC1=CC=C(CBr)C=C1 MKNQNPYGAQGARI-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
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- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5027—Polyphosphines
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
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- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
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- C—CHEMISTRY; METALLURGY
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- C07F9/58—Pyridine rings
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Abstract
本發明係關於式(I)之化合物
其中m及n各獨立地為0或1;R1、R2、R3、R4各係獨立地選自-(C1-C12)-烷基、-(C3-C12)-環烷基、-(C3-C12)-雜環烷基、-(C6-C20)-芳基、-(C3-C20)-雜芳基;R1、R2、R3、R4基團中之至少一者為-(C3-C20)-雜芳基;及R1、R2、R3、R4若為-(C1-C12)-烷基、-(C3-C12)-環烷基、-(C3-C12)-雜環烷基、-(C6-C20)-芳基或-(C3-C20)-雜芳基,其各可獨立地經一或更多選自下列之取代基取代:-(C1-C12)-烷基、-(C3-C12)-環烷基、-(C3-C12)-雜環烷基、-O-(C1-C12)-烷基、-O-(C1-C12)-烷基-(C6-C20)-芳基、-O-(C3-C12)-環烷基、-S-(C1-C12)-烷基、-S-(C3-C12)-環烷
基、-COO-(C1-C12)-烷基、-COO-(C3-C12)-環烷基、-CONH-(C1-C12)-烷基、-CONH-(C3-C12)-環烷基、-CO-(C1-C12)-烷基、-CO-(C3-C12)-環烷基、-N-[(C1-C12)-烷基]2、-(C6-C20)-芳基、-(C6-C20)-芳基-(C1-C12)-烷基、-(C6-C20)-芳基-O-(C1-C12)-烷基、-(C3-C20)-雜芳基、-(C3-C20)-雜芳基-(C1-C12)-烷基、-(C3-C20)-雜芳基-O-(C1-C12)-烷基、-COOH、-OH、-SO3H、-NH2、鹵素;以及關於其在烷氧基羰基化中作為配位子之用途。
Description
本發明係關於苯系雙膦化合物、此等化合物之金屬錯合物及其用於烷氧基羰基化的用途。
乙烯系不飽和化合物之烷氧基羰基化為重要性日益增加的製程。烷氧基羰基化被理解為意指乙烯系不飽和化合物(烯烴)與一氧化碳及醇類在金屬-配位子錯合物的存在下的反應以產生對應之酯類。典型地,所使用的金屬為鈀。下列流程圖顯示烷氧基羰基化的一般反應方程式:
在烷氧基羰基化反應(alkoxycarbonylation reaction)中,特別是乙烯與甲醇反應產生3-甲基丙酸酯之反應(乙烯甲氧基羰基化(ethene methoxycarbonylation))是
重要的作為製備甲基丙烯酸甲酯的中間步驟(S.G.Khokarale,E.J.García-Suárez,J.Xiong,U.V.Mentzel,R.Fehrmann,A.Riisager,Catalysis Communications 2014,44,73-75)。乙烯甲氧基羰基化是在作為溶劑的甲醇中於溫和條件下以經膦配位子修飾之鈀催化劑進行。
典型地,雙牙雙膦化合物在此係用作為配位子。一種非常好的催化劑系統是由Lucite-現在的Mitsubishi Rayon-所開發並使用基於1,2-雙(二-三級丁基膦基甲基)苯(DTBPMB)的配位子(W.Clegg,G.R.Eastham,M.R.J.Elsegood,R.P.Tooze,X.L.Wang,K.Whiston,Chem.Commun.1999,1877-1878)。
本發明所解決的問題係提供用於烷氧基羰基化之新穎的配位子,用其能達成較高的酯的產率。更特別的是,根據本發明之配位子係適合用於長鏈乙烯系不飽和化合物,例如C8烯烴,以及乙烯系不飽和化合物之混合物的烷氧基羰基化。亦容許有官能基的存在。
此問題係藉由經至少一個雜芳基取代在至少一個磷原子上的苯系雙膦化合物而解決。這些化合物特別適合於作為鈀錯合物之雙牙配位子並導致許多不同的乙烯系不飽和化合物之提高的烷氧基羰基化產率。根據本發明之配位子亦導致較低的作為副產物之醚的形成並改善烷氧基羰基化之正/異選擇性(n/iso selectivity)。
根據本發明之雙膦化合物為式(I)之化合物
其中m及n各獨立地為0或1;R1、R2、R3、R4各係獨立地選自-(C1-C12)-烷基、-(C3-C12)-環烷基、-(C3-C12)-雜環烷基、-(C6-C20)-芳基、-(C3-C20)-雜芳基;R1、R2、R3、R4基團中之至少一者為-(C3-C20)-雜芳基;及R1、R2、R3、R4若為-(C1-C12)-烷基、-(C3-C12)-環烷基、-(C3-C12)-雜環烷基、-(C6-C20)-芳基或-(C3-C20)-雜芳基,其各可獨立地經一或更多選自下列之取代基取代:-(C1-C12)-烷基、-(C3-C12)-環烷基、-(C3-C12)-雜環烷基、-O-(C1-C12)-烷基、-O-(C1-C12)-烷基-(C6-C20)-芳基、-O-(C3-C12)-環烷基、-S-(C1-C12)-烷基、-S-(C3-C12)-環烷基、-COO-(C1-C12)-烷基、-COO-(C3-C12)-環烷基、-CONH-(C1-C12)-烷基、-CONH-(C3-C12)-環烷基、-CO-(C1-
C12)-烷基、-CO-(C3-C12)-環烷基、-N-[(C1-C12)-烷基]2、-(C6-C20)-芳基、-(C6-C20)-芳基-(C1-C12)-烷基、-(C6-C20)-芳基-O-(C1-C12)-烷基、-(C3-C20)-雜芳基、-(C3-C20)-雜芳基-(C1-C12)-烷基、-(C3-C20)-雜芳基-O-(C1-C12)-烷基、-COOH、-OH、-SO3H、-NH2、鹵素。
在一個實施態樣中,根據本發明之雙膦化合物為式(II)及(III)中之一者的化合物
在這些式中,R1、R2、R3、R4基團各係如前文所定義。
措辭(C1-C12)-烷基包含具有1至12個碳原子之直鏈及支鏈烷基。這些較佳為(C1-C8)-烷基,更佳為(C1-C6)-烷基,最佳為(C1-C4)-烷基。
適合的(C1-C12)-烷基尤其是甲基、乙基、丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、正戊基、2-戊基、2-甲基丁基、3-甲基丁基、1,2-二甲基丙
基、1,1-二甲基丙基、2,2-二甲基丙基、1-乙基丙基、正己基、2-己基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、2,2-二甲基丁基、1,3-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基丁基、1-乙基-2-甲基丙基、正庚基、2-庚基、3-庚基、2-乙基戊基、1-丙基丁基、正辛基、2-乙基己基、2-丙基庚基、壬基、癸基。
關於措辭(C1-C12)-烷基之說明亦特別適用於-O-(C1-C12)-烷基、-S-(C1-C12)-烷基、-COO-(C1-C12)-烷基、-CONH-(C1-C12)-烷基、-CO-(C1-C12)-烷基及-N-[(C1-C12)-烷基]2中之烷基。
措辭(C3-C12)-環烷基包含具有3至12個碳原子之單-、雙-或三環烴基。較佳而言,這些基團為(C5-C12)-環烷基。
該(C3-C12)-環烷基較佳具有3至8個、更佳為5或6個環原子。
適合的(C3-C12)-環烷基尤其是環丙基、環丁基、環戊基、環己基、環庚基、環辛基、環十二基(cyclododecyl)、環十五基(cyclopentadecyl)、降莰基(norbornyl)、金剛烷基(adamantyl)。
關於措辭(C3-C12)-環烷基之說明亦特別適用於-O-(C3-C12)-環烷基、-S-(C3-C12)-環烷基、-COO-(C3-C12)-環烷基、-CONH-(C3-C12)-環烷基、-CO-(C3-C12)-環烷基中之環烷基。
措辭(C3-C12)-雜環烷基包含具有3至12個碳原子之非芳香族、飽和或部分不飽和環脂族基團,其中一或多個環碳原子係經雜原子置換。該(C3-C12)-雜環烷基較佳具有3至8個、更佳為5或6個環原子,且隨意地經脂族側鏈取代。在雜環烷基中,相對於環烷基,一或多個環碳原子係經雜原子或含雜原子基團置換。該雜原子或含雜原子基團較佳係選自O、S、N、N(=O)、C(=O)、S(=O)。在本發明上下文中之(C3-C12)-雜環烷基故而亦為乙烯氧化物(ethylene oxide)。
適合的(C3-C12)-雜環烷基尤其是四氫噻吩基(tetrahydrothiophenyl)、四氫呋喃基(tetrahydrofuryl)、四氫哌喃基(tetrahydropyranyl)及二烷基(dioxanyl)。
措辭(C6-C20)-芳基包含具有6至20個碳原子之單-或多環芳香族烴基。這些較佳為(C6-C14)-芳基,更佳為(C6-C10)-芳基。
適合的(C6-C20)-芳基尤其是苯基、萘基、茚基、茀基、蒽基、菲基、稠四苯基(naphthacenyl)、基(chrysenyl)、芘基、蔻基(coronenyl)。較佳之(C6-C20)-芳基為苯基、萘基及蒽基。
措辭(C3-C20)-雜芳基包含具有3至20個碳原子之單-或多環芳香族烴基,其中一或多個碳原子係經雜原子置換。較佳之雜原子為N、O及S。該(C3-C20)-雜芳基具有3至20、較佳為6至14、且更佳為6至10個環原子。因此,例如,在本發明上下文中之吡啶基為C6-雜芳
基;呋喃基為C5-雜芳基。
適合的(C3-C20)-雜芳基尤其是呋喃基、噻吩基、吡咯基、唑基、異唑基、噻唑基、異噻唑基、咪唑基、吡唑基、呋呫基(furazanyl)、四唑基、吡啶基、嗒基、嘧啶基、吡基、苯并呋喃基、吲哚基、異吲哚基、苯并咪唑基、喹啉基、異喹啉基。
措辭鹵素尤其包含氟、氯、溴及碘。特別較佳的是氟及氯。
在一個實施態樣中,R1、R2、R3、R4基團若為-(C1-C12)-烷基、-(C3-C12)-環烷基、-(C3-C12)-雜環烷基、-(C6-C20)-芳基、或-(C3-C20)-雜芳基,其各可獨立地經一或更多選自下列之取代基取代:-(C1-C12)-烷基、-(C3-C12)-環烷基、-(C3-C12)-雜環烷基、-O-(C1-C12)-烷基、-O-(C1-C12)-烷基-(C6-C20)-芳基、-O-(C3-C12)-環烷基、-S-(C1-C12)-烷基、-S-(C3-C12)-環烷基、-(C6-C20)-芳基、-(C6-C20)-芳基-(C1-C12)-烷基、-(C6-C20)-芳基-O-(C1-C12)-烷基、-(C3-C20)-雜芳基、-(C3-C20)-雜芳基-(C1-C12)-烷基、-(C3-C20)-雜芳基-O-(C1-C12)-烷基、-COOH、-OH、-SO3H、-NH2、鹵素。
在一個實施態樣中,R1、R2、R3、R4基團若為-(C1-C12)-烷基、-(C3-C12)-環烷基、-(C3-C12)-雜環烷基、-(C6-C20)-芳基、或-(C3-C20)-雜芳基,其各可獨立地經一或更多選自下列之取代基取代:-(C1-C12)-烷基、-(C3-C12)-環烷基、-O-(C1-C12)-烷基、-O-(C1-C12)-烷基-
(C6-C20)-芳基、-O-(C3-C12)-環烷基、-(C6-C20)-芳基、-(C6-C20)-芳基-(C1-C12)-烷基、-(C6-C20)-芳基-O-(C1-C12)-烷基、-(C3-C20)-雜芳基、-(C3-C20)-雜芳基-(C1-C12)-烷基、-(C3-C20)-雜芳基-O-(C1-C12)-烷基。
在一個實施態樣中,R1、R2、R3、R4基團若為-(C1-C12)-烷基、-(C3-C12)-環烷基、-(C3-C12)-雜環烷基、-(C6-C20)-芳基、或-(C3-C20)-雜芳基,其各可獨立地經一或更多選自下列之取代基取代:-(C1-C12)-烷基、-O-(C1-C12)-烷基-(C6-C20)-芳基、-(C3-C20)-雜芳基、-(C3-C20)-雜芳基-(C1-C12)-烷基、-(C3-C20)-雜芳基-O-(C1-C12)-烷基。
在一個實施態樣中,R1、R2、R3、R4基團若為-(C1-C12)-烷基、-(C3-C12)-環烷基、-(C3-C12)-雜環烷基、-(C6-C20)-芳基、或-(C3-C20)-雜芳基,其各可獨立地經一或更多選自下列之取代基取代:-(C1-C12)-烷基及-(C3-C20)-雜芳基。
在一個實施態樣中,R1、R2、R3、R4基團若為-(C1-C12)-烷基、-(C3-C12)-環烷基、或-(C3-C12)-雜環烷基,則係未經取代的,而若彼等為-(C6-C20)-芳基、或-(C3-C20)-雜芳基,則可以如所描述的經取代。
在一個實施態樣中,R1、R2、R3、R4基團若為-(C1-C12)-烷基、-(C3-C12)-環烷基、-(C3-C12)-雜環烷基、-(C6-C20)-芳基、或-(C3-C20)-雜芳基,則係未經取代的。
在一個實施態樣中,R1、R2、R3、R4各係獨立地選自-(C1-C12)-烷基、-(C6-C20)-芳基、-(C3-C20)-雜芳基;其中該R1、R2、R3、R4基團中之至少一者為-(C3-C20)-雜芳基;以及,R1、R2、R3、R4若為-(C1-C12)-烷基、-(C6-C20)-芳基或-(C3-C20)-雜芳基,其各可獨立地經一或更多上述取代基取代。
在一個實施態樣中,R1、R2、R3、R4基團中之至少二者為-(C3-C20)-雜芳基。
在一個實施態樣中,R1及R3基團各為-(C3-C20)-雜芳基且各可獨立地經一或更多上述取代基取代。較佳而言,R2及R4係獨立地選自-(C1-C12)-烷基、-(C3-C12)-環烷基、-(C3-C12)-雜環烷基、-(C6-C20)-芳基,更佳的是選自-(C1-C12)-烷基、-(C3-C12)-環烷基、-(C6-C20)-芳基,最佳的是選自-(C1-C12)-烷基。R2及R4可獨立地經一或更多上述取代基取代。
在一個實施態樣中,R1、R2、R3及R4基團為-(C6-C20)-雜芳基且各可獨立地經一或更多上述取代基取代。
在一個實施態樣中,R1、R2、R3及R4基團若為雜芳基,其各係獨立地選自具有五至十個環原子、較佳為五或六個環原子之雜芳基。
在一個實施態樣中,R1、R2、R3及R4基團若
為雜芳基,則其為具有五個環原子之雜芳基。
在一個實施態樣中,R1、R2、R3及R4基團若為雜芳基,則其各係獨立地選自具有六至十個環原子之雜芳基。
在一個實施態樣中,R1、R2、R3及R4基團若為雜芳基,則其為具有六個環原子之雜芳基。
在一個實施態樣中,R1、R2、R3及R4基團若為雜芳基,其係選自呋喃基、噻吩基、吡咯基、唑基、異唑基、噻唑基、異噻唑基、咪唑基、吡唑基、呋呫基(furazanyl)、四唑基、吡啶基、嗒基、嘧啶基、吡基、苯并呋喃基、吲哚基、異吲哚基、苯并咪唑基、喹啉基、異喹啉基,其中所提到的雜芳基可如上所述經取代。
在一個實施態樣中,R1、R2、R3及R4基團若為雜芳基,其係選自呋喃基、噻吩基、吡咯基、咪唑基、吡啶基、嘧啶基、吲哚基,其中所提到的雜芳基可如上所述經取代。
在一個實施態樣中,R1、R2、R3及R4基團若為雜芳基,其係選自2-呋喃基、2-噻吩基、2-吡咯基、2-咪唑基、2-吡啶基、2-嘧啶基、2-吲哚基,其中所提到的雜芳基可如上所述經取代。
在一個實施態樣中,R1、R2、R3及R4基團若為雜芳基,其係選自2-呋喃基、2-噻吩基、N-甲基-2-吡咯基、N-苯基-2-吡咯基、N-(2-甲氧苯基)-2-吡咯基、2-吡咯基、N-甲基-2-咪唑基、2-咪唑基、2-吡啶基、2-嘧啶
基、N-苯基-2-吲哚基、2-吲哚基,其中所提到的雜芳基不具有進一步的取代。
更佳而言,R1、R2、R3及R4基團若為雜芳基,則其為吡啶基,尤其是2-吡啶基。
在一個實施態樣中,R1及R3為吡啶基,較佳為2-吡啶基,且R2及R4為-(C1-C12)-烷基,其中R1、R2、R3及R4各可如上所述經取代。
在一個實施態樣中,根據本發明之雙膦化合物係選自式(1)及(18)中之一者:
本發明進一步係關於包含Pd及根據本發明之雙膦化合物的錯合物。在此等錯合物中,根據本發明之雙膦化合物用作金屬原子之雙牙配位子。該等錯合物用作
為,例如,烷氧基羰基化之催化劑。使用根據本發明之錯合物,其可能在許多不同的乙烯系不飽和化合物之烷氧基羰基化達成高產率。
根據本發明之錯合物亦可包含配位至金屬原子之另外的配位子。這些是,例如,乙烯系不飽和化合物或陰離子。適合的另外之配位子為,例如,苯乙烯、順丁烯二醯亞胺(例如,N-甲基順丁烯二醯亞胺(N-methylmaleimide))、1,4-萘醌(1,4-naphthoquinone)、乙酸根陰離子(acetate anion)、三氟乙酸根陰離子(trifluoroacetate anion)或氯陰離子。
本發明進一步係關於根據本發明之雙膦化合物(diphosphine compound)用於烷氧基羰基化反應(alkoxycarbonylation reaction)之催化的用途。根據本發明之化合物尤其能被用作為根據本發明之金屬錯合物。
本發明亦係關於包含下列方法步驟之方法:a)首先進料乙烯系不飽和化合物(ethylenically unsaturated compound);b)添加根據本發明之雙膦化合物及包含Pd之化合物,或添加包含Pd及根據本發明之雙膦化合物的根據本發明之錯合物;c)添加醇;d)饋入CO;e)加熱反應混合物,將該乙烯系不飽和化合物轉化
成酯。
在此方法中,方法步驟a)、b)、c)及d)能以任何所欲的順序進行。然而,典型地,CO的添加是在共反應物已首先在步驟a)至c)中進料後進行。步驟d)及e)能同時地或相繼地進行。此外,CO亦能於二或多個步驟饋入,以這樣的方式致使,例如,先饋入一部分的CO,然後加熱混合物,接著饋入另一部分的CO。
在根據本發明之方法中用作為反應物的乙烯系不飽和化合物含有一或多個碳-碳雙鍵。為了簡化,此等化合物在下文中亦稱作烯烴(olefin)。該等雙鍵可為末端(terminal)雙鍵或內(internal)雙鍵。
較佳的是具有2至30個碳原子之乙烯系不飽和化合物,較佳為2至22個碳原子,更佳為2至12個碳原子。
在一個實施態樣中,該乙烯系不飽和化合物包含2至30個碳原子,較佳為6至22個碳原子,更佳為8至12個碳原子,最佳為8個碳原子。
該乙烯系不飽和化合物除了一或多個雙鍵之外,還可含有另外的官能基。較佳而言,該乙烯系不飽和化合物包含一或多個選自下列的官能基:羧基、硫羧基(thiocarboxyl)、磺酸基、亞磺醯基(sulphinyl)、羧酸酐(carboxylic anhydride)基、醯亞胺基、羧酸酯基、磺酸酯(sulphonic ester)基、胺甲醯基、胺磺醯基(sulphamoyl)、氰基、羰基、硫羰基(carbonothioyl)、羥基、氫硫基
(sulphhydryl)、胺基、醚基、硫醚(thioether)基、芳基、雜芳基或矽基(silyl)及/或鹵素取代基。並且,該乙烯系不飽和化合物較佳包含總共2至30個碳原子,較佳為2至22個碳原子,更佳為2至12個碳原子。
在一個實施態樣中,該乙烯系不飽和化合物除了碳-碳雙鍵之外,不包含任何另外的官能基。
在一特別較佳的實施態樣中,該乙烯系不飽和化合物為具有至少一個雙鍵及2至30個碳原子、較佳為6至22個碳原子、更佳為8至12個碳原子、最佳為8個碳原子之非官能化烯烴(unfunctionalized alkene)。
適合的乙烯系不飽和化合物為,例如:乙烯;丙烯;C4烯烴例如1-丁烯、順-2-丁烯、反-2-丁烯、順-與反-2-丁烯之混合物、異丁烯、1,3-丁二烯;萃餘物(raffinate)I至III、裂解-C4(crack-C4)C5烯烴例如1-戊烯、2-戊烯、2-甲基-1-丁烯、2-甲基-2-丁烯、2-甲基-1,3-丁二烯(異戊二烯)、1,3-戊二烯;C6烯烴例如四甲基乙烯(tetramethylethylene)、1,3-己二烯、1,3-環己二烯;C7烯烴例如1-甲基環己烯、2,4-庚二烯、降莰二烯(norbornadiene);C8烯烴例如1-辛烯、2-辛烯、環辛烯、二正丁烯、二異丁烯、1,5-環辛二烯、1,7-辛二烯;
C9烯烴例如三聚丙烯(tripropene);C10烯烴例如二環戊二烯(dicyclopentadiene);十一烯;十二烯;內C14烯烴(internal C14 olefin);內C15至C18烯烴;直鏈或支鏈、環狀、非環狀或部分環狀、內C15至C30烯烴;三聚異丁烯(triisobutene)、三聚正丁烯(tri-n-butene);萜(terpene)類例如薴烯(limonene)、香葉草醇(geraniol)、菌綠烯醇(farnesol)、蒎烯(pinene)、月桂油烯(myrcene)、香芹酮(carvone)、3-蒈烯(3-carene);具有18個碳原子之多不飽和化合物,例如亞麻油酸(linoleic acid)或次亞麻油酸(linolenic acid);不飽和羧酸之酯類,例如乙酸或丙酸之乙烯酯、不飽和羧酸之烷基酯、丙烯酸及甲基丙烯酸之甲酯或乙酯、油酸酯(oleic ester)例如油酸甲酯或油酸乙酯、亞麻油酸或次亞麻油酸之酯類;乙烯系化合物例如乙酸乙烯酯、乙烯基環己烯(vinylcyclohexene)、苯乙烯、α-甲苯乙烯、2-異丙烯基萘(2-isopropenylnaphthalene);2-甲基-2-戊烯醛(2-methyl-2-pentenal)、3-戊烯酸甲酯(methyl 3-pentenoate)、甲基丙烯酸酐(methacrylic
anhydride)。
在本方法的一個變化型中,該乙烯系不飽和化合物係選自丙烯、1-丁烯、順-及/或反-2-丁烯、或其混合物。
在本方法的一個變化型中,該乙烯系不飽和化合物係選自1-戊烯、順-及/或反-2-戊烯、2-甲基-1-丁烯、2-甲基-2-丁烯、3-甲基-1-丁烯、或其混合物。
在一較佳實施態樣中,該乙烯系不飽和化合物係選自乙烯、丙烯、1-丁烯、順-及/或反-2-丁烯、異丁烯、1,3-丁二烯、1-戊烯、順-及/或反--2-戊烯、2-甲基-1-丁烯、3-甲基-1-丁烯、2-甲基-2-丁烯、己烯、四甲基乙烯、庚烯、正辛烯、1-辛烯、2-辛烯、或其混合物。
該乙烯系不飽和化合物可另選自1,7-辛二烯、環辛烯、10-十一烯酸甲酯(methyl 10-undecenoate)、1-甲基環己烯、5-己烯腈(5-hexenenitrile)、6-氯-1-己烯、乙烯基三乙基矽烷(vinyltriethylsilane)、香芹酮、異丙烯基苯(isopropenylbenzene)、4-氯異丙烯基苯(4-chloroisopropenylbenzene)、4-氟異丙烯基苯(4-fluoroisopropenylbenzene)、2-甲基異丙烯基苯(2-methylisopropenylbenzene)、2-異丙烯基萘(2-isopropenylnaphthalene)、1,1-二苯乙烯(1,1-diphenylethylene)、1,3-二異丙烯基苯(1,3-
diisopropenylbenzene)、、四甲基乙烯、N-
乙烯酞醯亞胺(N-vinylphthalimide)、2,3,4,5,6-五氟苯乙
烯、,,,、
反-2-丁烯酸乙酯(ethyl trans-2-butenoate)。
在一個變化型中,使用了乙烯系不飽和化合物之混合物。在本發明上下文中之混合物係指包含至少二種不同的乙烯系不飽和化合物之組成物,其中個別乙烯系不飽和化合物各者之比例,以混合物之總重為基準計,較佳為至少5重量%。
較佳的是使用各具有2至30個碳原子、較佳為4至22個碳原子、更佳為6至12個碳原子、最佳為8至10個碳原子之乙烯系不飽和化合物的混合物。
適合的乙烯系不飽和化合物之混合物是稱為萃餘物I至III的那些。萃餘物I包含40%至50%異丁烯、20%至30% 1-丁烯、10%至20%順-和反-2-丁烯、高至1% 1,3-丁二烯及10%至20%正丁烷和異丁烷。萃餘物II是從萃餘物I移除異丁烯後之於輕油裂解(naphtha cracking)產生之C4餾分(C4 fraction)的一部分且基本上由異構(isomeric)正丁烯、異丁烷及正丁烷所組成。萃餘物III係於輕油裂解產生之C4餾分的一部分且基本上由異構正丁烯及正丁烷所組成。
另一適合的混合物為二正丁烯,也稱為二丁烯、DNB或DnB。二正丁烯為C8烯烴之異構物混合物,
其係從1-丁烯、順-2-丁烯及反-2-丁烯之混合物的二聚合(dimerization)產生。在工業中,萃餘物II或萃餘物III物流通常進行催化低聚合(catalytic oligomerization),其中所存在的丁烷(正/異)無改變的脫出(emerge),而所存在的烯烴被完全或部分轉化。而且通常亦形成二聚二正丁烯(dimeric di-n-butene)、更高級低聚物(higher oligomer)(三聚丁烯(tributene)C12、四聚丁烯(tetrabutene)C16),其等係在反應後藉由蒸餾移除。這些同樣可用作為反應物。
在較佳之變化型中,使用了包含異丁烯、1-丁烯、順-及反-2-丁烯之混合物。較佳而言,混合物係包含1-丁烯、順-及反-2-丁烯。
根據本發明之烷氧基羰基化係藉由根據本發明之Pd錯合物催化。Pd錯合物可在方法步驟b)中以包含Pd及根據本發明之膦配位子之預先形成的錯合物而添加,或可由包含Pd之化合物及游離膦配位子(free phosphine ligand)原位(in situ)形成。在本上下文中,包含Pd之化合物亦稱為催化劑前驅物(catalyst precursor)。
在催化劑係原位形成的情況下,可加入過量的配位子,使得反應混合物中亦存在有未結合的配位子。
而在錯合物係在一開始就添加的情況下,亦可添加另外的配位子,使得在反應混合物中亦存在有未結合的配位子。
在一個變化型中,包含Pd之化合物係選自氯
化鈀(PdCl2)、乙醯丙酮鈀(II)[Pd(acac)2]、乙酸鈀(II)[Pd(OAc)2]、二氯(1,5-環辛二烯)鈀(II)[Pd(cod)2Cl2]、雙(二亞苄丙酮)鈀(bis(dibenzylideneacetone)palladium)[Pd(dba)2]、雙(乙腈)二氯化鈀(II)[Pd(CH3CN)2Cl2]、(桂皮基)二氯化鈀(palladium(cinnamyl)dichloride)[Pd(cinnamyl)Cl2]。
較佳而言,包含Pd之化合物為PdCl2、Pd(acac)2或Pd(OAc)2。特別適合的是PdCl2。
在方法步驟c)中之醇可為支鏈或直鏈、環狀、非環狀、部分環狀或脂族,且尤其是C1-至C30-烷醇。有可能使用一元醇(monoalcohol)或多元醇(polyalcohol)。
方法步驟c)中之醇較佳包含1至30個碳原子,更佳為1至22個碳原子,尤佳為1至12個碳原子。其可以是一元醇或多元醇。
除了一或多個羥基之外,醇還可含有另外的官能基。較佳而言,醇可另外包含一或多個選自下列之官能基:羧基、硫羧基(thiocarboxyl)、磺酸基、亞磺醯基(sulphinyl)、羧酸酐(carboxylic anhydride)基、醯亞胺基、羧酸酯基、磺酸酯(sulphonic ester)基、胺甲醯基、胺磺醯基(sulphamoyl)、氰基、羰基、硫羰基(carbonothioyl)、氫硫基(sulphhydryl)、胺基、醚基、硫醚(thioether)基、芳基、雜芳基或矽基及/或鹵素取代基。
在一個實施態樣中,醇除了羥基之外不包含
任何另外的官能基。
醇可含有不飽和及芳香族基團。然而,其較佳為脂族醇。
在本發明上下文中之脂族醇係指不包含任何芳香族基團的醇,即,例如,烷醇、烯醇(alkenol)或炔醇。
在一個實施態樣中,醇為具有一或多個羥基及1至30個碳原子、較佳為1至22個碳原子、更佳為1至12個碳原子、最佳為1至6個碳原子之烷醇。
在本方法的一個變化型中,方法步驟c)中之醇係選自一元醇的群組。
在本方法的一個變化型中,方法步驟c)中之醇係選自:甲醇、乙醇、1-丙醇、異丙醇、異丁醇、三級丁醇、1-丁醇、2-丁醇、1-戊醇、2-戊醇、3-戊醇、1-己醇、環己醇、酚、2-乙基己醇、異壬醇、2-丙基庚醇。
在較佳之變化型中,方法步驟c)中之醇係選自:甲醇、乙醇、1-丙醇、1-丁醇、1-戊醇、1-己醇、2-丙醇、三級丁醇、3-戊醇、環己醇、酚、及其混合物。
在本方法的一個變化型中,方法步驟c)中之醇係選自多元醇的群組。
在本方法的一個變化型中,方法步驟c)中之醇係選自:二元醇、三元醇、四元醇(tetraol)。
在本方法的一個變化型中,方法步驟c)中之醇係選自:環己-1,2-二醇、乙-1,2-二醇、丙-1,3-二醇、甘
油、丁-1,2,4-三醇、2-羥基甲基丙-1,3-二醇、1,2,6-三羥基己烷、新戊四醇、1,1,1-三(羥基甲基)乙烷、兒茶酚(catechol)、間苯二酚(resorcinol)及羥氫醌(hydroxyhydroquinone)。
在本方法的一個變化型中,方法步驟c)中之醇係選自:蔗糖、果糖、甘露糖、山梨糖(sorbose)、半乳糖及葡萄糖。
在本方法之一較佳實施態樣中,方法步驟c)中之醇係選自:甲醇、乙醇、1-丙醇、1-丁醇、1-戊醇、1-己醇。
在本方法之一特佳的變化型中,方法步驟c)中之醇係選自:甲醇、乙醇。
在本方法之一特佳的變化型中,方法步驟c)中之醇為甲醇。
在本方法的一個變化型中,方法步驟c)中之醇係以過量使用。
在本方法的一個變化型中,方法步驟c)中之醇係同時用作為溶劑。
在本方法的一個變化型中,使用了另外的溶劑,其係選自:甲苯、二甲苯、四氫呋喃(THF)及二氯甲烷(CH2Cl2)。
在步驟d)中CO較佳係在CO分壓介於0.1和10MPa(1至100巴)之間,較佳為介於1和8MPa(10至80巴)之間,更佳為介於2和4MPa(20至40巴)之間饋
入。
在根據本發明之方法的步驟e)中反應混合物係加熱至較佳為介於10℃和180℃之間的溫度,較佳為介於20和160℃之間、更佳為介於40和120℃之間,以便將乙烯系不飽和化合物轉化成酯。
首先在步驟a)中所進料的乙烯系不飽和化合物與在步驟c)中所添加的醇之莫耳比較佳係介於1:1和1:20之間,更佳為介於1:2至1:10之間,更佳為介於1:3至1:4之間。
Pd與首先在步驟a)中所進料的乙烯系不飽和化合物之質量比較佳係介於0.001重量%和0.5重量%之間,較佳為介於0.01重量%和0.1重量%之間,更佳為介於0.01重量%和0.05重量%之間。
根據本發明之雙膦化合物與Pd之莫耳比較佳係介於0.1:1和400:1之間,較佳為介於0.5:1和400:1之間,更佳為介於1:1和100:1之間,最佳為介於2:1和50:1之間。
較佳而言,添加酸來進行該方法。在一個變化型中,該方法因此另外包含步驟c'):添加酸到反應混合物中。此較佳可為布忍斯特酸(Brønsted acid)或路易斯酸(Lewis acid)。
適合的布忍斯特酸較佳具有pKa 5之酸強度,較佳為pKa 3之酸強度。所記述之酸強度pKa係基於在標準條件(25℃,1.01325巴)所測定之pKa。在多質子
酸的情況,本發明上下文中之酸強度pKa係關於第一質子解(protolysis)步驟之pKa。
較佳而言,該酸不為羧酸。
適合的布忍斯特酸為,例如,過氯酸、硫酸、磷酸、甲膦酸(methylphosphonic acid)及磺酸。較佳而言,該酸是硫酸或磺酸。適合的磺酸為,例如,甲磺酸(methanesulphonic acid)、三氟甲磺酸(trifluoromethanesulphonic acid)、三級丁磺酸(tert-butanesulphonic acid)、對甲苯磺酸(p-toluenesulphonic acid,PTSA)、2-羥基丙-2-磺酸(2-hydroxypropane-2-sulphonic acid)、2,4,6-三甲苯磺酸(2,4,6-trimethylbenzenesulphonic acid)及十二基磺酸(dodecylsulphonic acid)。特佳的酸為硫酸、甲磺酸、三氟甲磺酸及對甲苯磺酸。
所使用的路易斯酸可為,例如,三氟甲磺酸鋁(aluminium triflate)。
在一個實施態樣中,在步驟c')中酸的添加量,以在步驟a)中所使用之乙烯系不飽和化合物的莫耳量為基準計,為0.3至40mol%,較佳為0.4至15mol%,更佳為0.5至5mol%,最佳為0.6至3mol%。
圖1:二正丁烯用配位子1在120℃及40巴之甲氧基羰基化。
圖2:二正丁烯用配位子1在100℃及12巴之甲氧基羰基化。
實施例
下列實施例說明了本發明。
一般步驟
所有下列製備均係在保護氣體下使用標準Schlenk技術進行。溶劑在使用前於適當乾燥劑上乾燥(Purification of Laboratory Chemicals,W.L.F.Armarego(Author),Christina Chai(Author),Butterworth Heinemann(Elsevier),6th edition,Oxford 2009)。
三氯化磷(Aldrich)於使用前在氬氣下蒸餾。所有製備操作均在烘乾容器(baked-out vessel)中進行。產物係藉由NMR光譜法定性。化學位移(δ)係以ppm記述。31P NMR信號係引用如下:SR31P=SR1H * (BF31P/BF1H)=SR1H * 0.4048。(Robin K.Harris,Edwin D.Becker,Sonia M.Cabral de Menezes,Robin Goodfellow,and Pierre Granger,Pure Appl.Chem.,2001,73,1795-1818;Robin K.Harris,Edwin D.Becker,Sonia M.Cabral de Menezes,Pierre Granger,Roy E.Hoffman and Kurt W.Zilm,Pure Appl.Chem.,2008,80,59-84)。
核共振光譜之記錄係以Bruker Avance 300或
Bruker Avance 400進行,氣相層析分析係以Agilent GC 7890A進行,元素分析係以Leco TruSpec CHNS和Varian ICP-OES 715進行,而ESI-TOF質譜法係以Thermo Electron Finnigan MAT 95-XP和Agilent 6890 N/5973儀器進行。
氯-2-吡啶基-三級丁基膦(前驅物A)的製備
用於合成氯-2-吡啶基-三級丁基膦(chloro-2-pyridyl-t-butylphosphine)之格任亞(Grignard)係以異丙基氯化鎂(isopropylmagnesium chloride)藉由"Knochel方法"製備(Angew.Chem.2004,43,2222-2226)。該處理係根據Budzelaar之方法進行(Organometallics 1990,9,1222-1227)。
將8.07ml之1.3M異丙基氯化鎂溶液(Knochel試劑)導入具有磁攪拌器和隔膜之50ml圓底燒瓶中,並冷卻到-15℃。其後,迅速滴加953.5μl(10mmol)之2-溴吡啶。該溶液立即變黃。允許其升溫至-10℃。反應之轉化率(conversion)係測定如下:取約100μl溶液並
將其導入1ml之飽和氯化銨溶液中。若溶液"冒泡",則還沒有很多格任亞(Grignard)形成。該水溶液以吸量管之***萃取,而有機相經Na2SO4乾燥。記錄醚溶液(ethereal solution)的GC。當與2-溴吡啶相較已形成大量的吡啶時,轉化率是高的。在-10℃,已有少量的轉化。在升溫至室溫並攪拌1-2小時後,反應溶液變成黃棕色。GC測試顯示完全轉化。此時可用注射泵將格任亞溶液緩慢滴加到預先已冷卻到-15℃之1.748g(11mmol)二氯三級丁基膦於10ml THF中之溶液中。重要的是該二氯三級丁基膦(dichloro-tert-butylphosphine)溶液是經冷卻的。在室溫下,會得到相當大量的二吡啶基三級丁基膦(dipyridyl-tert-butylphosphine)。最初形成黃色澄清溶液,然後變混濁。讓該混合物升溫至室溫並攪拌過夜。根據GC-MS,已形成大量的產物。在高真空下移除溶劑,便得到在有些地方為棕色的帶白色固體。將該固體用20ml之庚烷懸浮,並於超音波浴中粉碎該固體。使該白色固體沉澱出來後,倒出溶液。以每次10-20ml之庚烷重複該操作二次。在高真空下濃縮庚烷溶液後,於減壓下蒸餾。在4.6毫巴(mbar)、油浴120℃及蒸餾溫度98℃下,可蒸餾該產物。得到1.08g無色的油。(50%)。
分析數據:1H NMR(300MHz,C6D6):δ 8.36(m,1H,Py),7.67(m,1H,Py),7.03-6.93(m,1H,Py),6.55-6.46(m,1H,Py),1.07(d,J=13.3Hz,9H,t-Bu)。
13C NMR(75MHz,C6D6):δ 162.9,162.6,
148.8,135.5,125.8,125.7,122.8,35.3,34.8,25.9及25.8。
31P NMR(121MHz,C6D6)δ 97.9。
MS(EI)m:z(相對強度)201(M+,2),147(32),145(100),109(17),78(8),57.1(17)。
化合物1(α,α‘-雙(2-吡啶基(三級丁基)膦基)鄰二甲苯)的製備
(Lit:Graham Eastham等人,專利US 6335471)
在手套箱中,稱出675mg(27.8mmol,4eq)之鎂粉於具有氮氣接頭(nitrogen tap)和磁攪拌棒之250ml圓底燒瓶中,然後以隔膜(septum)密封燒瓶。將高真空施加到該圓底燒瓶(約5×10-2毫巴)並將其加熱到90℃歷經45分鐘。冷卻到室溫後,加入2粒碘再將該混合物溶於20ml之THF中。攪拌該懸浮液約10分鐘直到碘的黃色消失。在鎂粉沉澱出來後,倒出混濁的THF溶液,然後以1-2ml的THF清洗活化的鎂粉二次。接著加入另外20ml的新鮮THF。在室溫下,用注射泵緩慢滴加1.21g(6.9
mmol)α,α'-二氯-鄰-二甲苯(α,α'-dichloro-o-xylene)於70ml THF中之溶液。該THF溶液漸漸變成深色。次日,過濾該THF懸浮液以移除未轉化的鎂粉,然後測定格任亞化合物(Grignard compound)之成分如下:將1ml之格任亞溶液於NH4Cl飽和水溶液中驟冷再以***萃取。經Na2SO4乾燥後,記錄該***溶液之GC。在定性方面,觀察到只形成鄰二甲苯。
格任亞溶液之成分的定量測定:將1ml之格任亞溶液以2ml之0.1M HCl驟冷,並以0.1M NaOH滴定過量的酸。適合的指示劑為0.04%溴甲酚(bromocresol)水溶液。顏色從黃變藍。已消耗掉0.74ml之0.1M NaOH。2ml-0.74ml=1.26ml,其相當於0.126mmol之格任亞化合物。由於有二格任亞(di-Grignard)存在,該格任亞溶液為0.063M。此係超過90%的產率。
在具有回流冷凝器和磁攪拌器之250ml三頸燒瓶中,於氬氣下,將1.8g(8.66mmol)之氯膦(2-Py(tBu)PCl)溶於10ml之THF中並冷卻到-60℃。然後在此溫度下用注射泵緩慢滴加55ml之上述所規定的格任亞溶液(0.063M,3.46mmol)。該溶液起初維持澄清然後變成鮮黃色。1.5小時之後,該溶液變混濁。留置該混合物升溫至室溫過夜然後得到黃色澄清溶液。為了完成反應,將該混合物在回流下加熱1小時。冷卻後,加入1ml之H2O,然後該溶液失去顏色並且變成乳白色。在高真空下
移除THF之後,得到黏的淡黃色固體。於其中加入10ml水和10ml***,得到具有良好可分性(separability)的二均勻澄清相。水相以***萃取兩次。在有機相已用Na2SO4乾燥後,於高真空下移除***,然後得到黏的幾乎無色的固體。將後者溶於5ml之MeOH中同時於水浴中加熱,然後用矽藻土(Celite)過濾。在-28℃下隔夜獲得772mg呈白色結晶形式之產物。(51%)。濃縮後,可能從母液分離另外100mg。總產率為57.6%。
1H NMR(300MHz,C6D6):δ 8.58(m,2H,Py),7.31-7.30(m,2H,苯),7.30-7.22(m,2H,Py),6.85-6.77(m,2H,Py),6.73(m,2H,苯),6.57-6.50(m,2H,py),4.33(dd,J=13.3及4.3Hz,2H,CH2),3.72-3.62(m,2H,CH2),121(d,J=11.8Hz,18H,tBu),13C NMR(75MHz,C6D6):δ 161.3,161.1,149.6,137.8,137.7,134.5,133.3,132.7,131.4,131.3,125.7,122.9,30.7,30.5,28.2,28.0,26.5,26.4,26.2及26.1。
31P NMR(121MHz,C6D6)δ 8.8,C26H34N2P2之EA計算值:C,71.54;H,7.85;N,6.56;P,14.35,實測值:C,71.21;H,7.55;N,6.56;P,14.35。
化合物18(1-(2-吡啶基(三級丁基)膦基)-2-(2-吡啶基(三級丁基)膦基甲基)苯)的製備
於手套箱中,稱取675mg(27.8mmol,4eq)之鎂粉到具有氮氣接頭和磁攪拌棒的250ml之圓底燒瓶中,然後以隔膜密封燒瓶。將高真空施加到該圓底燒瓶(約5×10-2毫巴)並將其加熱到90℃歷經45分鐘。冷卻到室溫後,加入2粒碘再將該混合物溶於20ml之THF中。攪拌該懸浮液約10分鐘直到碘的黃色消失。在鎂粉沉澱出來後,倒出混濁的THF溶液,然後以1-2ml的THF清洗活化的鎂粉二次。接著加入另外20ml的新鮮THF。在室溫下,用注射泵緩慢滴加920.7μl(6.9mmol)氯化2-溴苄基(2-bromobenzyl chloride)於70ml THF中之溶液。該THF溶液變混濁且帶輕微的綠色。次日,呈現帶綠色乳狀懸浮液。待過量的Mg粉沉澱出來之後,倒出懸浮液,然後測定格任亞化合物的成分:將1ml之格任亞溶液以2ml之0.1M HCl驟冷,並以0.1M NaOH滴定過量的酸。適合的指示劑為0.04%溴甲酚水溶液。顏色從黃變藍。已消耗掉0.4ml之0.1M NaOH。2ml-0.4ml=1.6ml,其相當於0.15mmol之格任亞化合物。由於有二格任亞(di-Grignard)存在,該
格任亞溶液為0.075M。
在具有回流冷凝器之250ml三頸燒瓶中,於氬氣下,將2.64g(13.12mol,2.5eq)之氯膦(2-Py(tBu)PCl)溶於15ml之THF中並冷卻到-60℃。然後在此溫度下用注射泵緩慢滴加70ml之奶綠色格任亞溶液(0.075M,5.25mmol)。在滴加的三個小時期間,反應溶液未見有顯著的變化。留置該混合物升溫至室溫過夜然後得到深黃色澄清溶液。為了完成反應,將該混合物在回流下加熱2小時。冷卻後,於其中加入1ml之H2O,然後在高真空下移除THF。得到黏的帶黃色固體。之後,於其中加入20ml水和30ml***,然後得到具有不良相分離之非均勻(inhomogeneous)溶液。藉由添加無水甲醇(absolute methanol),可能促進相分離。水相以***萃取二次。合併的***相是澄清的黃色。在抽出***後,獲得2.1g淡橙色粗產物。後者不能從甲醇結晶。為了純化該產物,將膦轉化成對應的硼烷加成物(borane adduct):將粗產物溶於15ml THF中,並將11.55ml(2.3eq)之1M硼烷/THF複合物一次性全部加入。讓混合物在室溫下攪拌一天,然後用Combi-Flash裝置以對硼烷加成物進行層析(chromatograph)(乙酸乙酯/庚烷=1:10)。獲得1.18g(52%)之白色多孔固體。從光譜上明顯看出一定有2個非鏡像異構物(diastereomer)存在:1H NMR(400MHz,CDCl3):δ 8.76及8.73(m,2H,arom),8.10(m,1H,arom),7.92-7.62(m,3H,arom),
7.40(m,2H,arom),7.31(m,1H,arom),4.22-3.92(m,2H,CH2),1.51(d,J=14.5Hz,tBu,3H),1.45(d,J=14.5Hz,tBu,6H),1.23(d,J=14.5Hz,3H,tBu),1.22(d,J=14.5Hz,tBu,6H)。
31P NMR(161MHz,CDCl3)δ 37.71(d,寬,J=52.8Hz),36.52(d,寬,J=52.9Hz),33.65(s,寬),31.90(s,寬)。
為了得到游離膦,將該硼烷加成物溶於20ml之啉中並加熱到50℃歷經4小時。之後,在高真空下移除啉,然後在氬氣下對殘留物進行層析。(乙酸乙酯/庚烷=1:2)。產物在前面流出管柱因此能容易地被分離。再次移除溶劑,然後獲得1.1g(98%)無色黏性油。在光譜中,再次觀察到呈1:2之比例的二個非鏡像異構物。
1H NMR(300MHz,C6D6):δ 8.65,8.57及8.51(m,2H,arom),7.58及7.51-7.33(m,4H,arom),7.01及7.02-6.76(m,4H,arom),6.63-6.45(m,2H,arom),4.84,4.47,4.23及3.80(m,2H,CH2),1.53(d,J=12.8Hz,3H,tBu),1.51(d,J=12.8Hz,6H,tBu),1.27-1.15(m,9H,tBu)。
13C NMR(75MHz,C6D6):δ 167.2,167.0,149.7,149.2,149.0,148.9,137.1,136.7,136.3,134.2,134.1,133.2,132.6,130.2,130.1,130.0,129.6,129.5,129.2,128.8,125.6,122.7,122.5,120.8,120.6(arom),33.2,33.0,32.1,31.4,31.2(q,tBu),29.2,28.9,28.4,28.2,
28.1,27.9(tBu),27.6,27.3(CH2),22.9,14.2。
31P NMR(121MHz,C6D6)δ 17.90(d,J=29.2Hz),16.13(d,J=21.9Hz),-0.59(d,J=21.9Hz),-0.73(d,J=29.2Hz)。
C25H32N2P2之元素分析計算值:C,71.07;H,7.63;N,6.63;P,14.66。實測值:C,71.15;H,8.20;N,6.63;P,14.94。
配位子
在下列烷氧基羰基化實驗中,使用下列配位子:配位子1,發明實施例
配位子18,發明實施例
配位子3,1,2-雙(二-三級丁基膦基甲基)苯(DTBPMB),比較實施例
高壓實驗
原料:二正丁烯亦如下所述稱為:二丁烯、DNB或DnB。
二正丁烯為C8烯烴之異構物混合物,其係從1-丁烯、順-2-丁烯及反-2-丁烯之混合物的二聚合產生。在工業中,萃餘物II或萃餘物III物流通常進行催化低聚合,其中所存在的丁烷(正/異)無改變的脫出(emerge),而所存在的烯烴被完全或部分轉化。而且通常亦形成二聚二正丁烯、更高級低聚物(三聚丁烯C12、四聚丁烯
C16),其等係在反應後必須藉由蒸餾移除。
另一種在工業上所實施用於C4烯烴之低聚合的方法稱為"OCTOL方法"。
在專利文獻中,DE102008007081A1,例如,描述基於OCTOL方法之低聚合。EP1029839A1是關於在OCTOL方法中所形成之C8烯烴的分餾。
工業二正丁烯通常組成為達5%至30%正辛烯、45%至75% 3-甲基庚烯,及達10%至35%的3,4-二甲基己烯。較佳之物流含有10%至20%正辛烯、55%至65% 3-甲基庚烯、及15%至25% 3,4-二甲基己烯。
對甲苯磺酸係簡寫如下:pTSA、PTSA或p-TSA。在本文中PTSA總是指對甲苯磺酸一水合物(para-toluenesulphonic acid monohydrate)。
實行高壓實驗的一般方法
批式模式之反應的一般實驗說明:適當量的基質、鈀鹽、酸及醇在氬氣下於50ml Schlenk容器中混合,同時以磁攪拌器攪拌。
配備有進氣和出氣閥、數位壓力轉換器、溫度感測器和球閥、及安裝的取樣用毛細管之來自Parr的100ml鋼製高壓釜藉由真空及氬氣吹掃三次來清除氧。隨後,於氬氣逆流(argon counterflow)中將來自Schlenk容器的反應溶液藉由毛細管導入高壓釜中(通過球閥)。其後,在室溫下注入適量CO然後將高壓釜加熱升溫至反應
溫度(在恆壓下不進行的反應),或是先將高壓釜加熱升溫至反應溫度然後藉由連接至高壓釜的量管(burette)注入CO(利用減壓器(pressure reducer))。接著將此量管以CO充填至約100巴,而且在反應期間以恆壓供應所需的CO。此量管具有約30ml的怠體積(dead volume)並配備有數位壓力轉換器。然後在所需溫度下進行反應達所需時間,同時予以攪拌。在此過程中,利用軟體(來自SpecView公司的Specview)及Parr 4870程序控制器和4875功率調節器,記錄高壓釜和氣體量管(gas burette)中之壓力變化數據。利用這些數據產生Excel表,其在後期用來產生顯示隨時間之氣體消耗及因此之轉化率的圖表。若需要,經由毛細管,收集並分析GC樣本。為此目的,在反應前亦將適合的精確量(2-10ml)之異辛烷作為內標準物加入到Schlenk容器中。這些亦給予關於反應過程的資訊。反應結束時,將高壓釜冷卻至室溫,小心地釋放壓力,如有必要則加入異辛烷作為內標準物(internal standard),然後進行GC分析,或在新產物的情況下進行GC-MS分析。
在玻璃小瓶中之高壓釜實驗的一般實驗方法:使用300ml Parr反應器。與此相配的是已在內部(in-house)製造且適於以習用磁攪拌器(例如來自Heidolph)加熱之對應尺寸的鋁塊。關於高壓釜的內部,製造厚約1.5cm的圓形金屬板,其含有對應於玻璃小瓶之
外徑的6個孔洞。配合這些玻璃小瓶,其等配備有小的磁攪拌器。這些玻璃小瓶配備有螺帽(screw cap)和適合的隔膜,並使用由吹玻璃機(glass blower)所製造的專用裝置在氬氣下進料適當的反應物、溶劑和催化劑以及添加劑。為此目的,同時充填6個容器;這使得能夠在一個實驗中實施在相同溫度和相同壓力下的6個反應。然後這些玻璃容器以螺帽和隔膜蓋上,並使用適合尺寸之小的注射器套管來穿刺各個隔膜。這使得在反應後期能夠氣體交換。接著將這些小瓶置於金屬板中,並在氬氣下將這些轉移到高壓釜中。高壓釜以CO吹掃並在室溫下以所欲CO壓力充填。然後,藉由磁攪拌器,於磁攪拌下,將高壓釜加熱到反應溫度並進行反應一段適當的時間。隨後,將高壓釜冷卻到室溫並緩慢釋放壓力。其後,高壓釜以氮氣吹掃。從高壓釜取出小瓶,並加入一定量之適合的標準物。進行GC分析,其結果用來決定產率及選擇率。
在12-小瓶高壓釜(600ml Parr高壓釜)中的實驗之一般方法:於每個烘乾的玻璃小瓶首先進料二正丁烯(DnB)和甲醇,然後加入Pd(acac)2(0.5mg,0.0016mmol)和配位子(0.0064mmol)於0.2ml甲醇中之溶液,H2SO4(溶液:1ml之H2SO4於50ml MeOH中)亦然。在高壓釜中,混合物以10巴之CO吹掃二次,將CO注入達所欲壓力,並在所欲溫度下攪拌該混合物20h。反應結束後,在每一情況中加入異辛烷(內標準物)及1ml之EtOAc。用
GC分析有機相。
藉由GC(異辛烷作為內標準物)測定反應產率。
分析
來自乙烯之產物的GC分析:關於GC分析,使用具有30m HP管柱之Agilent 7890A氣相層析儀。溫度剖面圖(Temperature profile):35℃、10min;10℃/min至200℃、16.5min;注入體積為1μl,分流(split)為50:1。丙酸甲酯之滯留時間:6.158min
來自四甲基乙烯(tetramethylethene)之產物的GC分析:關於GC分析,使用具有30m HP管柱之Agilent 7890A氣相層析儀。溫度剖面圖:35℃、10min;10℃/min至200℃、16.5min;注入體積為1μl,分流為50:1。
四甲基乙烯(tetramethylethylene)和產物的滯留時間:7.436min
***的滯留時間:11.391min
3,4-二甲基戊酸甲酯(methyl 3,4-dimethylpentanoate)的滯留時間:17.269min
二正丁烯的GC分析:關於GC分析,使用具有30m HP5管柱之Agilent 7890A氣相層析儀。溫度剖面圖:35℃、10min;10℃/min至200℃;注入體積為1μl,分流為50:1。
二正丁烯和產物的滯留時間:10.784-13.502min
從二正丁烯形成之酯類在下文中稱為MINO(異壬酸甲酯(methyl isononanoate))。
未知異構物之***產物的滯留時間分布:15.312、17.042、17.244、17.417min
異-C9酯類的滯留時間19.502-20.439min(主峰:19.990min)
正-C9酯類的滯留時間:20.669、20.730、20.884、21.266min。
實驗的評估
關於催化實驗的評估,在下文中使用容許比較不同催化劑系統之特定指示劑。
TON:轉換數(turnover number),係定義為每莫耳催化劑金屬之產物莫耳數,其為對催化錯合物之生產率的度量。
TOF:轉換頻率(turnover frequency),係定義為用於達到特定轉換率,例如50%,之每單位時間的TON。TOF為對催化系統之活性的度量。
在下文中所記述的正選擇率(n selectivity)係關於末端甲氧基羰基化之比例,以甲氧基羰基化產物之總產率為基準計。
正/異比(n/iso ratio)表示末端轉化(converted terminally)成為酯類之烯烴(olefin)與內部轉化(converted
internally)成為酯類之烯烴的比率。
乙烯之甲氧基羰基化
a)配位子1
25ml鋼製高壓釜在氬氣下進料PdCl2(2.53mg,0.04mol%)、1(24.9mg,0.16mol%)及MeOH(5ml)。然後將乙烯(1g,35.7mmol)導入高壓釜中(藉由秤監測質量)。將高壓釜加熱升溫至80℃(壓力約20巴),接著注入CO至30巴。在80℃進行反應20小時。
其後,將高壓釜冷卻至室溫並解除壓力。將內容物轉移到50ml Schlenk燒瓶,並加入異辛烷(5ml)作為GC內標準物。藉由GC分析測定產率。(產率:>99%)。
b)配位子18
在氬氣下,於100ml鋼製高壓釜進料Pd(acac)2(6.52mg,0.04mol%)和配位子18(36.1mg,0.16mol%)及PTSA(61.1mg,0.6mol%)及甲醇(20ml)。然後將1.5g(53.6mmol)之乙烯(3.5來自Linde AG)轉移
到高壓釜中。(監測高壓釜的質量)。在高壓釜已加熱升溫至80℃的反應溫度後(壓力約10巴),於此溫度下注入CO(30巴)。在此溫度下,進行反應20小時。然後將高壓釜冷卻至室溫並解除壓力。將內容物轉移到50ml Schlenk容器中,並加入異辛烷(內標準物,5.0ml)。藉由GC分析測定產率及選擇率。(產率:92%)。
本發明之配位子1及18因此在乙烯之甲氧基羰基化上達到高產率。
四甲基乙烯在PTSA的存在下之甲氧基羰基化
a)反應溫度:100℃
(i)配位子3(比較實施例)
於25ml Schlenk容器進料[Pd(acac)2](4.87mg,0.1mol%)、對甲苯磺酸(PTSA)(24.32mg,0.8mol%)及MeOH(8ml)。於4ml小瓶進料3(6.3mg,0.4mol%),並加入磁攪拌棒。其後,以注射器加入2ml之黃色澄清溶液及四甲基乙烯(478μl,4mmol)。將小瓶放到試樣架中,其進而在氬氣氣氛下***300ml Parr高壓釜
中。在高壓釜已以氮氣吹掃三次後,將CO壓力調整到40巴。在100℃進行反應20小時。反應一結束,將高壓釜冷卻至室溫並小心地解除壓力。加入異辛烷(200μl)作為GC內標準物。藉由GC測定產率及位置選擇性(regioselectivity)。(轉化率:40%,無酯產物產率;醚產物產率38%)。
(ii)配位子1
於25ml Schlenk容器進料[Pd(acac)2](4.87mg,0.1mol%)、對甲苯磺酸(PTSA)(24.32mg,0.8mol%)及MeOH(8ml)。於4ml小瓶進料1(7.0mg,0.4mol%),並加入磁攪拌棒。其後,以注射器加入2ml之黃色澄清溶液及四甲基乙烯(478μl,4mmol)。將小瓶放到試樣架中,其進而在氬氣氣氛下***300ml Parr高壓釜中。在高壓釜已以氮氣吹掃三次後,將CO壓力調整到40巴。在100℃進行反應20小時。反應一結束,將高壓釜冷卻至室溫並小心地解除壓力。加入異辛烷(200μl)作為GC內標準物。藉由GC測定產率及位置選擇性。(轉化率:82%,酯產物產率:60%;醚產物產率20%)。
b)反應溫度:120℃
(i)配位子3(比較實施例)
於25ml Schlenk容器進料[Pd(acac)2](4.87mg,0.1mol%)、對甲苯磺酸(PTSA)(24.32mg,0.8mol%)
及MeOH(8ml)。於4ml小瓶進料3(6.3mg,0.4mol%),並加入磁攪拌棒。其後,以注射器加入2ml之黃色澄清溶液及四甲基乙烯(478μl,4mmol)。將小瓶放到試樣架中,其進而在氬氣氣氛下***300ml Parr高壓釜中。在高壓釜已以氮氣吹掃三次後,將CO壓力調整到40巴。在120℃進行反應20小時。反應一結束,將高壓釜冷卻至室溫並小心地解除壓力。加入異辛烷(200μl)作為GC內標準物。藉由GC測定產率及位置選擇性。(轉化率:54%,無酯產物產率;醚產物產率52%)。
(ii)配位子1
於25ml Schlenk容器進料[Pd(acac)2](4.87mg,0.1mol%)、對甲苯磺酸(PTSA)(24.32mg,0.8mol%)及MeOH(8ml)。於4ml小瓶進料1(7.0mg,0.4mol%),並加入磁攪拌棒。其後,以注射器加入2ml之黃色澄清溶液及四甲基乙烯(478μl,4mmol)。將小瓶放到試樣架中,其進而在氬氣氣氛下***300ml Parr高壓釜中。在高壓釜已以氮氣吹掃三次後,將CO壓力調整到40巴。在120℃進行反應20小時。反應一結束,將高壓釜冷卻至室溫並小心地解除壓力。加入異辛烷(200μl)作為GC內標準物。藉由GC測定產率及位置選擇性。(轉化率:>99%,酯產物產率:98%;無醚產物產率)。
如可以從結果推斷出,配位子1,甚至在100℃及40巴的CO壓力下,導致比比較配位子3更高的酯
產物產率。此外,使用配位子1,形成較低比例之副產物(醚)。
四甲亞基(tetramethylene)在三氟甲磺酸的存在下之甲氧基羰基化
在氬氣下,於100ml鋼製高壓釜進料Pd(acac)2(4.87mg,0.04mol%)、配位子1(28.0mg,0.16mol%)及CF3SO2OH(72.1mg,1.28mol%)。然後,在氬氣下,加入MeOH(20ml)、異辛烷(5ml)及四甲基乙烯(4.8ml,40mmol)。高壓釜於室溫下進料40巴之CO。在120℃進行反應20小時。於此期間,用安裝在高壓釜中之HPLC閥及高壓釜中之內部毛細管,在不同的時間採取樣本。藉由GC分析來分析這些樣本並測定預期的產物之產率。取樣結束後,將高壓釜冷卻並解除壓力,然後採取進一步最終的GC樣本並將其用來測定產率。(98% 3,4-二甲基戊酸甲酯之產率)。
二正丁烯在PTSA的存在下之甲氧基羰基化
二正丁烯為具有8個碳原子之不同的烯烴異構物的混合物。其來源和一般組成已經闡明如上。所使用的DnB含有約16%(w/w)正辛烯、65%甲基庚烯及19%二甲基己烯。
將二正丁烯與甲醇反應以產生異壬酸甲酯(MINO)。
烷氧基羰基化的目的是為了在直鏈產物上於中到高選擇率下達到非常好的產率,並且最終對工業方法達到良好的時空產率(space-time yield),以短的反應時間升至最終產率。
配位子1:100ml鋼製高壓釜在氬氣下進料Pd(acac)2(5.85mg,0.04mol%)、1(33.5mg,0.16mol%)、MeOH(20ml)、7.54ml二正丁烯(48mmol)及PTSA(對甲苯磺酸一水合物)(54.7mg,0.6mol%)。然後於室溫下將CO注入高壓釜中至40巴。在120℃進行反應20小時。反應後,將高壓釜冷卻至室溫並釋放壓力。將5ml之異辛烷加入該溶液中作為內標準物。藉由GC分析測定產率及選擇率。(產率:96%,正/異(n/iso):73:27)。
圖1顯示關於此反應之產率對時間之繪圖。
配位子3(比較實施例):100ml鋼製高壓釜在氬氣下進料[Pd(acac)2](5.85mg,0.04mol%)及3(30.3mg,0.16mol%)。隨後,加入MeOH(30ml)和二正丁烯(7.54ml,48mmol)及PTSA(54.7mg,0.6mol%)。在室溫下於高壓釜進料純度為4.7之CO至40巴並在120℃進行反應20小時。其後,將高壓釜冷卻並緩慢釋放壓力。將高壓釜的內容物轉移到Schlenk容器。加入5ml之異辛烷作為內標準,然後藉由GC分析測定產率及選擇率(MINO之產率60%,正/異:93/7)。
這些實驗顯示本發明之配位子1在二正丁烯之甲氧基羰基化上達成了比比較配位子3更高的產率。
二正丁烯在硫酸的存在下之甲氧基羰基化
配位子1:在各個情況下於烘乾之Schlenk燒瓶首先進料0.04mol%之Pd(acac)2(15mg)及0.16mol%之1(105mg)。然後加入12.4ml(300mmol)之甲醇(工業級)、18.8ml(120mmol)之二正丁烯及32μl(0.5mol%)之H2SO4(98%),並將混合物轉移到100ml高壓釜。高壓釜接著以10巴之CO吹掃二次,進料CO至6巴並加熱至100℃。然後高壓釜藉由氣體量管進料CO至12巴,並在100℃於恆定CO壓力(12巴)下攪拌20h。反應結束後,加入異辛烷(內標準物)及10ml之EtOAc。藉由GC分析有機相。產率為91%,正選擇率(n selectivity)79%。
氣體消耗曲線圖顯示於圖2。
如可以從該圖推斷出,反應在20小時後實質上完成。約20巴的氣體吸收相當於91%的產率。
乙烯及二正丁烯在H
2
的存在下之甲氧基羰基化
下列實驗顯示,當使用根據本發明之配位子時,乙烯或二正丁烯之甲氧基羰基化的產率並未由於CO氣體受到H2之污染而顯著減少。根據本發明之方法因此亦能在少量H2的存在下進行。
a)使用配位子1之乙烯的甲氧基羰基化
在氬氣氣氛下,於100ml鋼製高壓釜進料
Pd(acac)2(6.5mg,0.04mol%)、1(37.7mg,0.16mol%)、PTSA(61.1mg,0.6mol%)及MeOH(20ml)。然後將乙烯(3.5Linde)(1.5g,53.6mmol)轉移到高壓釜中(藉由秤監測質量)。在室溫下將H2(3巴)和CO(30巴)導入高壓釜中。接著在80℃進行反應20小時。隨後,將高壓釜冷卻並解除壓力。將內容物轉移到50ml Schlenk容器,並加入異辛烷(內標準物,3.0ml)。藉由GC分析測定產率。(丙酸甲酯之產率:99%)。
b)使用配位子1之二正丁烯的甲氧基羰基化
100ml鋼製高壓釜在氬氣下進料Pd(acac)2(5.8mg,0.04mol%)、配位子1(33.5mg,0.16mol%)及PTSA(54.7mg,0.6mol%)。然後在氬氣下加入MeOH(30ml)及二正丁烯(7.54ml,48mmol)。在室溫下於高壓釜進料H2(3巴)和CO(40巴)。在120℃反應20小時後,將高壓釜冷卻並解除壓力。將內容物轉移到50ml Schlenk容器,並加入異辛烷(內標準物,8ml)。藉由GC分析測定產率及位置選擇性(產率:94%,正/異:74/26)。
使用配位子3及1之各種烯烴的甲氧基羰基化
配位子3(比較實施例)之反應條件:在氬氣下,於25ml Schlenk容器進料由[Pd(acac)2](12.2mg,0.04mol)、3(63.1mg,0.16mmol)、PTSA(114mg,0.6mmol)及MeOH(25ml)所構成的儲備溶液。於配備有磁攪
拌器之4ml玻璃小瓶進料2mmol之烯烴。以注射器向其加入1.25ml事先製備的儲備溶液。在氬氣下將此小瓶置於300ml Parr高壓釜中的金屬板上。高壓釜以CO吹掃三次接著注入CO至40巴。然後在磁攪拌下,於120℃進行反應20h。其接著冷卻並逐漸釋放壓力。加入0.2ml之異辛烷作為內標準物。藉由GC和GC-MS分析測定轉化率及產率。
配位子1之反應條件:在氬氣下,於25ml Schlenk容器進料由[Pd(acac)2](12.2mg,0.04mol)、1(69.8mg,0.16mmol)、PTSA(114mg,0.6mmol)及MeOH(25ml)所構成的儲備溶液。於配備有磁攪拌器之4ml玻璃小瓶進料2mmol之烯烴。以注射器向其加入1.25ml事先製備的儲備溶液。在氬氣下將此小瓶置於300mlParr高壓釜中的金屬板上。高壓釜以CO吹掃三次接著注入CO至40巴。然後在磁攪拌下,於120℃進行反應20h。其接著冷卻並逐漸釋放壓力。加入0.2ml之異辛烷作為內標準物。藉由GC和GC-MS分析測定轉化率及產率。
關於GC分析,在兩個例子中,均使用具有30m HP管柱之Agilent 7890A氣相層析儀。溫度剖面圖:35℃,10min;10℃/min至285℃,285℃ 5min;注入體積為1μl,分流為50:1。
結果顯示於下列二個表中。
表3:用配位子3(比較實施例)及1(發明之
配位子)之基質篩選(substrate screening)
如結果顯示,可藉由根據本發明之方法轉化許多不同的乙烯系不飽和化合物。在大多數情況下,本發明之配位子1顯示了比比較配位子3更好的酯產率、更低的異構化程度(isomerization level)、更低的副產物形成以及更好的正/異選擇性(n/iso selectivity)。
Claims (14)
- 一種式(I)之化合物,其中m及n各獨立地為0或1;R1及R3各為-(C3-C20)-雜芳基;R2及R4各係獨立地選自-(C1-C12)-烷基、-(C3-C12)-環烷基、-(C3-C12)-雜環烷基、-(C6-C20)-芳基、-(C3-C20)-雜芳基;及R1、R2、R3、R4若為-(C1-C12)-烷基、-(C3-C12)-環烷基、-(C3-C12)-雜環烷基、-(C6-C20)-芳基或-(C3-C20)-雜芳基,其各可獨立地經一或更多選自下列之取代基取代:-(C1-C12)-烷基、-(C3-C12)-環烷基、-(C3-C12)-雜環烷基、-O-(C1-C12)-烷基、-O-(C1-C12)-烷基-(C6-C20)-芳基、-O-(C3-C12)-環烷基、-S-(C1-C12)-烷基、-S-(C3-C12)-環烷基、-COO-(C1-C12)-烷基、-COO-(C3-C12)-環烷基、-CONH-(C1-C12)-烷基、-CONH-(C3-C12)-環烷基、-CO-(C1-C12)-烷基、-CO-(C3-C12)-環烷基、-N-[(C1-C12)-烷基]2、-(C6-C20)-芳基、-(C6-C20)-芳基-(C1-C12)-烷基、-(C6-C20)-芳基-O-(C1-C12)-烷基、-(C3-C20)-雜芳基、-(C3-C20)-雜芳基-(C1-C12)-烷基、-(C3-C20)-雜芳基-O-(C1-C12)-烷基、-COOH、-OH、-SO3H、-NH2、鹵素。
- 根據申請專利範圍第1或2項之化合物,其中,該R2及R4基團中之至少一者為-(C3-C20)-雜芳基。
- 根據申請專利範圍第1項之化合物,其中,R2及R4各係獨立地選自-(C1-C12)-烷基、-(C3-C12)-環烷基、-(C3-C12)-雜環烷基、-(C6-C20)-芳基。
- 根據申請專利範圍第1項之化合物,其中,R2及R4各係獨立地選自-(C1-C12)-烷基。
- 一種包含Pd及根據申請專利範圍第1至7項中任一項之化合物的錯合物。
- 一種烷氧基羰基化之方法,其包含下列方法步驟:a)首先進料乙烯系不飽和化合物;b)添加根據申請專利範圍第1至7項中任一項之化合物及包含Pd之化合物,或添加根據申請專利範圍第8項之錯合物;c)添加醇;d)饋入CO;e)加熱反應混合物,將該乙烯系不飽和化合物轉化成酯。
- 根據申請專利範圍第9項之方法,其中,該乙烯系不飽和化合物包含2至30個碳原子及隨意的一或多個選自下列之官能基:羧基、硫羧基(thiocarboxyl)、磺酸基、亞磺醯基(sulphinyl)、羧酸酐(carboxylic anhydride)基、醯亞胺基、羧酸酯基、磺酸酯(sulphonic ester)基、胺甲醯基、胺磺醯基(sulphamoyl)、氰基、羰基、硫羰基(carbonothioyl)、羥基、氫硫基(sulphhydryl)、胺基、醚基、硫醚(thioether)基、芳基、雜芳基或矽基及/或鹵素取代基。
- 根據申請專利範圍第9或10項之方法,其中,該乙烯系不飽和化合物係選自:乙烯、丙烯、1-丁烯、順-及/或反-2-丁烯、異丁烯、1,3-丁二烯、1-戊烯、順-及/或反-2-戊烯、2-甲基-1-丁烯、3-甲基-1-丁烯、2-甲基-2-丁烯、己烯、四甲基乙烯、庚烯、1-辛烯、2-辛烯、二正丁烯、及其混合物。
- 根據申請專利範圍第9項之方法,其中,在方法步驟b)中之該包含Pd之化合物係選自:二氯化鈀、乙醯丙酮鈀(II)、乙酸鈀(II)、二氯(1,5-環辛二烯)鈀(II)、雙(二亞苄丙酮)鈀(bis(dibenzylideneacetone)palladium)、雙(乙腈)二氯化鈀(II)、(桂皮基)二氯化鈀(palladium(cinnamyl)dichloride)。
- 根據申請專利範圍第9項之方法,其中,在方法步驟c)中之該醇係選自:甲醇、乙醇、1-丙醇、1-丁醇、1-戊醇、1-己醇、2-丙醇、三級丁醇、3-戊醇、環己醇、酚、及其混合物。
- 一種根據申請專利範圍第1至7項中任一項之化合物或根據申請專利範圍第8項之錯合物的用途,其係用於烷氧基羰基化反應(alkoxycarbonylation reaction)之催化。
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