CN1249022C - 氰戊酸或其酯的制备方法 - Google Patents
氰戊酸或其酯的制备方法 Download PDFInfo
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- CN1249022C CN1249022C CNB998103802A CN99810380A CN1249022C CN 1249022 C CN1249022 C CN 1249022C CN B998103802 A CNB998103802 A CN B998103802A CN 99810380 A CN99810380 A CN 99810380A CN 1249022 C CN1249022 C CN 1249022C
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- China
- Prior art keywords
- group
- unsubstituted
- alkyl
- aryl
- halogen
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- 150000002148 esters Chemical class 0.000 title claims abstract description 15
- NICLKHGIKDZZGV-UHFFFAOYSA-N 2-cyanopentanoic acid Chemical compound CCCC(C#N)C(O)=O NICLKHGIKDZZGV-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 4
- -1 palladium (II) compound Chemical class 0.000 claims abstract description 74
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Natural products C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000003446 ligand Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 150000002825 nitriles Chemical class 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
- 125000004442 acylamino group Chemical group 0.000 claims description 7
- 125000004423 acyloxy group Chemical group 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000002521 alkyl halide group Chemical group 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 5
- 125000001118 alkylidene group Chemical group 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000004437 phosphorous atom Chemical group 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 claims 3
- UVKXJAUUKPDDNW-NSCUHMNNSA-N (e)-pent-3-enenitrile Chemical compound C\C=C\CC#N UVKXJAUUKPDDNW-NSCUHMNNSA-N 0.000 abstract description 12
- ISBHMJZRKAFTGE-ONEGZZNKSA-N (e)-pent-2-enenitrile Chemical compound CC\C=C\C#N ISBHMJZRKAFTGE-ONEGZZNKSA-N 0.000 abstract description 3
- LCJODIDSNGYYSQ-UHFFFAOYSA-N 1-phosphanyl-n-(phosphanylmethyl)methanamine Chemical compound PCNCP LCJODIDSNGYYSQ-UHFFFAOYSA-N 0.000 abstract 1
- 150000001450 anions Chemical class 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 12
- 239000001294 propane Substances 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 238000005810 carbonylation reaction Methods 0.000 description 10
- 229910052763 palladium Inorganic materials 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- UEMGWPRHOOEKTA-UHFFFAOYSA-N 1,3-difluorobenzene Chemical compound FC1=CC=CC(F)=C1 UEMGWPRHOOEKTA-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 6
- ISBHMJZRKAFTGE-UHFFFAOYSA-N pent-2-enenitrile Chemical compound CCC=CC#N ISBHMJZRKAFTGE-UHFFFAOYSA-N 0.000 description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 4
- XGWFJBFNAQHLEF-UHFFFAOYSA-N 9-anthroic acid Chemical compound C1=CC=C2C(C(=O)O)=C(C=CC=C3)C3=CC2=C1 XGWFJBFNAQHLEF-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 150000002940 palladium Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- SKUPALMUTWEAPI-UHFFFAOYSA-N 5-cyanopentanoic acid Chemical compound OC(=O)CCCCC#N SKUPALMUTWEAPI-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- LQJBNNIYVWPHFW-QXMHVHEDSA-N gadoleic acid Chemical class CCCCCCCCCC\C=C/CCCCCCCC(O)=O LQJBNNIYVWPHFW-QXMHVHEDSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000007306 turnover Effects 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- CCFAKBRKTKVJPO-UHFFFAOYSA-N 1-anthroic acid Chemical compound C1=CC=C2C=C3C(C(=O)O)=CC=CC3=CC2=C1 CCFAKBRKTKVJPO-UHFFFAOYSA-N 0.000 description 2
- MBIZFBDREVRUHY-UHFFFAOYSA-N 2,6-Dimethoxybenzoic acid Chemical compound COC1=CC=CC(OC)=C1C(O)=O MBIZFBDREVRUHY-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
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000004646 arylidenes Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- URYYVOIYTNXXBN-UHFFFAOYSA-N cyclooctene Chemical compound [CH]1[CH]CCCCCC1 URYYVOIYTNXXBN-UHFFFAOYSA-N 0.000 description 2
- 239000004913 cyclooctene Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 125000003010 ionic group Chemical group 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 2
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 2
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane Chemical compound CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- 150000000191 1,4-naphthoquinones Chemical class 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- FFFIRKXTFQCCKJ-UHFFFAOYSA-N 2,4,6-trimethylbenzoic acid Chemical compound CC1=CC(C)=C(C(O)=O)C(C)=C1 FFFIRKXTFQCCKJ-UHFFFAOYSA-N 0.000 description 1
- PSCITZRLRGWIHI-UHFFFAOYSA-N 2-(4-aminophenyl)pyridin-3-ol Chemical compound C1=CC(N)=CC=C1C1=NC=CC=C1O PSCITZRLRGWIHI-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- ZDULHUHNYHJYKA-UHFFFAOYSA-N 2-propan-2-ylsulfonylpropane Chemical compound CC(C)S(=O)(=O)C(C)C ZDULHUHNYHJYKA-UHFFFAOYSA-N 0.000 description 1
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- HXWADCAVTSNWIJ-UHFFFAOYSA-N CCCCCC(CC)SP(O)(O)=S.CN(C)C Chemical compound CCCCCC(CC)SP(O)(O)=S.CN(C)C HXWADCAVTSNWIJ-UHFFFAOYSA-N 0.000 description 1
- QNWGJTDBZOBYGN-UHFFFAOYSA-N CCCCCCCCC.[O] Chemical class CCCCCCCCC.[O] QNWGJTDBZOBYGN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910021529 ammonia Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical group CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明关系于一种制备氰戊酸或其酯的方法,其包括:将2-,3-或4-戊烯腈或其混合物于催化剂系统存在下,与一氧化碳及羟基化合物反应,该催化剂系统包括:(i)钯(II)化合物,(ii)二齿二膦配位体,及(iii)阴离子来源。本发明还涉及新颖的催化剂系统,其中包括双(膦基甲基)胺型的二膦配位体。
Description
本发明系关于一种制备氰戊酸或其酯的方法,其中包括于催化剂系统存在下,将2-,3-或4-戊烯腈或其混合物与一氧化碳及羟基化合物反应。
5-氰戊酸及其酯可做为染料,杀害虫剂,纤维,特别是聚酰胺纤维以及塑料的原料。使其氢化后得到6-氨基己酸或是6-氨基己酸酯,将其去水或醇后,可获得己内酰胺。
已知于催化剂存在下将戊烯腈进行羰基化反应以生成氰戊酸及氰戊酸酯的方法。已知的合成法包括于催化剂系统存在下,在高温高压下,在水或醇存在下,将戊烯腈与一氧化碳反应。所使用的催化剂系统主要是钴化合物,如,CO2(CO)8或Co(OAc)2,以及含氮碱(参见GB-1 497 046及DE-2 541 640),特殊的溶剂,如,环砜烷(参见US 4 508 660),环酰胺或是尿素衍生物(参见EP-373 579)或是腈类(参见EP-377 838及US 4 933 483)。
EP 0 450 577中描述以Rh/HI催化剂系统对戊烯腈进行羟基羰基化反应以生成氰戊酸。
腈化合物通常与过渡金属形成络合物。具有催化剂活性的催化剂络合物于腈配位后就失去了活性。这样的现象对钯尤其明显,因为钯极易于生成稳定的腈络合物,如,(PhCN)2PdCl2,(CH3CN)2PdCl2。因此以钯催化含腈的烯烃进行羰基化反应通常以极低的催化剂活性进行。例如,US 4257973描述以催化剂系统(Ph3P)2PdCl2/SnCl2对3-戊烯腈进行羰基化反应。该反应以未知的选择性进行,非专一性氰酸酯的产率仅有5%(参见US 4 257 973的实例108)。
EP 0 495 547叙述于包括钯阳离子,二齿(bidentate)二膦配位体及阴离子来源的催化剂系统存在下,对任选取代的烯烃不饱和化合物进行单羰基化反应。根据EP 0 495 547,原料烯烃可经如,氰基或是腈基团取代。当以烯酸衍生物,如,烯腈做为原料时,较佳的,该烯酸衍生物是2-烯酸衍生物。对烯酸衍生物进行羰基化反应时,较佳的,催化剂系统中包括促进剂,如醌及硝基化合物。EP 0 495 547的实例59于Pd(OAc)2,TBPD(1,3-双(二-正-丁基膦基)丙烷),NiTFS(二-三氟甲基磺酸镍)及1,4-萘醌存在下,将丙烯腈与一氧化碳及甲醇进行羰基化反应。不过,依所使用的丙烯腈,转换为丙二酸之单甲酯单腈仅有5%。由EP 0 495 547,本领域技术人员可预期到利用本处的方法,以丙烯腈之外的经腈基取代的烯烃进行反应所得的产率更低。
令人惊讶的是,我们已经发现到利用与EP 0 495 547相比拟的催化剂系统对2-,3-,或4-戊烯腈进行羰基化反应,可获得高产率及高选择性。我们已经发现新颖的催化剂系统及新颖的二膦配位体,可进一步提高其产率及选择性。
因此,本发明可提供制备氰戊酸或其酯的方法,其中包括:将2-,3-,或4-戊烯腈或其混合物于催化剂系统存在下,与一氧化碳及羟基化合物反应,该催化剂系统包括:(i)钯(II)化合物,(ii)二齿二膦配位体,及(iii)阴离子来源。
在本发明用在羰基化反应的原料是2-,3-,或4-戊烯腈或其混合物。其中以使用包括3-及/或4-戊烯腈为主要成份的3-及/或4-戊烯腈或其混合物为佳。其中又以包括3-戊烯腈为主要成份的3-戊烯腈或其混合物为佳。根据德国OPI文件1 593 277,2 344 767及2 009470描述的方法,例如于镍络合物或是氯化铜(I)的存在下,3-戊烯腈的制备可利用将氢氰酸加成到丁二烯上来进行。
不论所使用的2-,3-,或4-戊烯腈或其混合物,本发明方法提供高选择性的5-氰戊酸。我们相信2-戊烯腈和3-戊烯腈先进行异构反应生成4-戊烯腈。由4-戊烯腈以本发明方法进行羰基化反应生成5-氰戊酸或其酯基本上区域选择性地进行,其选择性,根据生成的氰戊酸或其酯,一般系高于70%,较佳高于80%。
钯(II)化合物以钯盐为佳。适当的钯盐实例包括硝酸盐,硫酸盐,磺酸盐,如氯磺酸盐,甲基磺酸盐,三氟甲基磺酸盐,叔丁基磺酸盐,对甲苯磺酸盐,或是经磺酰化离子交换树脂,或是羧酸盐,如,烷酸,例,醋酸或是三氟醋酸的盐。已知当钯(II)化合物是适当的酸的钯盐,该化合物可用做本发明之阴离子来源。钯(II)化合物也可是钯络合物,如,与二齿二膦配位体生成络合物。如此,钯(II)化合物即自然包括根据本发明所用的二齿二膦配位体。钯(II)化合物也可以由元素态在反应中生成。
钯(II)化合物的用量并不重要。较佳的,其用量是对每摩耳所用戊烯腈由10-7至10-1摩耳的钯,特别是由10-6至10-2摩耳。
二齿二膦配位体可直接使用,或是与钯(II)化合物生成络合物使用。较佳的,二膦配位体系如下通式:
R1R2P-X-PR3R4
其中的R1,R2,R3及R4独立地是C1-C20-烷基,C3-C10-环烷基,芳基或是具有最高达4个稠合芳环的杂芳基,C7-C20-芳烷基,其各自可经取代,或是R1及R2及/或R3及R4共为C2-C20-亚烷基,亚芳基或具有最高达4个芳环的亚杂芳基或是C7-C20-亚芳烷基,其各自可经取代,且X是二价的桥键基团,其使得两翼的磷原子经1-10个原子分隔。
较佳的,二膦配位体中,R1,R2,R3及R4分别独立地是具有1-10个碳原子基团之未经取代,直链或具支链,直链或环烷基基团,或是R1及R2及/或R3及R4共为具有1-10个碳原子基团之,直链或具支链,直链或环状亚烷基基团。
较佳的,R1,R2,R3及R4分别选自甲基,乙基,丙基,异丙基,正丁基,仲丁基,叔丁基及/或环己基基团。或是R1及R2及/或R3及R4共为五亚甲基,六亚甲基或是亚环辛基基团。如上述,R1,R2,R3或R4均可经取代,该取代基可是任何不损害该系统催化剂活性的取代基。适当的取代基包括卤素原子,烷氧基,卤烷基,卤烷氧基,酰基基团,酰基氧基基团,氨基基团,羟基,腈基,酰基氨基,及芳基。
根据本发明所使用的二膦配位体是二齿(bidentate);也就是说,其必须包含两个膦基的磷原子维持在分子内的距离,同时,在分子内的结构上,必须使得两个磷原子与单一的钯原子生成配位键。因此,在上述优选结构式中,X是二价的桥键基团,其使得两翼的磷原子经1-10个原子分隔。较佳的,该桥键基中不包括任何在立体上会阻碍配位进行的取代基。较佳的,X是可包括杂原子的亚烷基链,如二价烃,醚或硫醚基团。桥键基X的实例,如,-CH2-,-CH2CH2-,-CH2CH2CH2-,-CH2OCH2-,-CH2SCH2-,-CH2CH2CH2CH2-,-CH2CH2OCH2CH2-,-CH2CH2SCH2CH2-,-CH2CH2OCH2CH2OCH2CH2-,-CH2C(CH3)2-CH2-,-CH2-CH(CH3)-O-CH(CH3)-CH2-。
因此,适当的二齿二膦配位体的实例是:
1,2-双(二-正-丁基膦基)乙烷,
1,3-双(二甲基膦基)丙烷,
1,3-双(二异丙基膦基)丙烷,
1,3-双(二-正-丙基膦基)丙烷,
1,3-双(二异丁基膦基)丙烷,
1,3-双(二-正-丁基膦基)丙烷,
1,3-双(二-仲丁基膦基)丙烷,
1,3-双(二-叔丁基膦基)丙烷,
1,3-双(二-正-己基膦基)丙烷,
1,2-双(二-环己基膦基)乙烷,
1,3-双(正-丁基甲基膦基)丙烷,
1,3-双(正-丁基乙基膦基)丙烷,
1,3-双(1,5-亚环辛基膦基)丙烷,及其包括1,4-亚环辛基基团的异构混合物,
1,4-双(二异丙基膦基)丁烷,
1,5-双(二甲基膦基)-3-氧杂戊烷,
1,8-双(二-正-丁基膦基)-3,6-二氧辛烷,及
1,4-双(二-正-丁基膦基)-2,2,3,3-四甲基丁烷。
较佳的实施方案中,X是
-CH2-N(R5)-CH2-
其中R5是氢,直链或是具支链的C1-C20-烷基,如,甲基,乙基,正-丙基,异丙基,正-丁基,仲丁基,叔丁基,戊基,己基,辛基,未经取代或是经C1-C6-烷基取代之C3-C10-环烷基,包括双环烷基,如,环丙基,环戊基,环己基,降冰片烷基(norbornyl),蒎烷基,冰片基,双环壬基,未经取代或是经C1-C6-烷基取代之C6-C20-芳基,如,苯基,甲苯基,萘基,未经取代或是经C1-C6-烷基取代之C7-C20-芳烷基,如,在烷基基团上具有1-6个碳原子,及在芳基基团上具有6-14个碳原子,如苯甲基,未经取代或是经C1-C6-烷基取代之C3-C20-杂芳基,如,吡啶基,嘧啶基,吡嗪基,三嗪基,或是C2-C21-酰基。
若上述基团可经C1-C6-烷基取代,其可经一个或多个烷基所取代,例,甲基或乙基。
前述基团可经一个或多个,例,由1-5个选自下述的取代基所取代,其中包括-NO,-NO2,-CN,-CO2 -,-CO2R6,-CONR6 2,卤素,即,F,Cl,Br,I,-NR6 2,-OR6,-NR6+ 3,-SO3 -,-SO3R6,-SO2R6,SO2NR6 2,及SiR7 3,其中R6是氢,C1-C10-烷基,特别是甲基,乙基,或是异丙基,或是C6-C14-芳基,特别是苯基,且R7是C1-C10-烷基,特别是甲基,乙基,或是异丙基,或是C6-C14-芳基,特别是苯基。尤其是在前述基团中,1,2,3或4碳原子可经N或O所取代。
R5是如-(CH2)n-Q的基团,其可经取代,且可包括杂原子,如,氧或氮,或是在亚烷基链中的亚芳基单位,如亚苯基,其中Q是-SO3 -,CO2 -,CO2R6,-CONR6 2,卤素,-NR6 2,-OR6,NR6+ 3,且n=1-20,较佳为1-10,R5是SiR7 3,如,三甲基甲硅烷基,叔丁基二甲基甲硅烷基,三苯基甲硅烷基。
较佳的,R5是亲电子基团,因为这可提高二膦化合物的稳定性。适当的亲电子基团R5是至少经一种亲电子基团所取代的直链或是具支链的C1-C20-烷基,较佳的,该亲电子基团位于α-,β-,γ-及/或δ-位置,特别是相对于氮原子之α-及/或β-位置,至少经一种亲电子基团所取代的C6-C14-芳基,以及腈,亚磺酰基(-SO2R7),磺酰基(-SO3R7),及硝基。R5可以是-C(O)R8,其中R8是直链或是具支链的C1-C20-烷基,C6-C14-芳基或是于烷基部分具有1-10个碳原子及于芳基部分具有6-14个碳原子的芳烷基,及至少经一个亲电子基团取代的直链或是具支链的C1-C20-烷基,较佳的,该亲电子基团系位于相对C(O)基团之α-,β-,γ-及/或δ-位置,以及至少经一个亲电子基团取代的C6-C14-芳基。较佳的R8基团包括甲基,乙基,异丙基,苯基,三氟甲基苯基,三氟甲基或五氟乙基。
在烷基或芳基R5上的适当亲电子取代基是卤素原子,如氟,氯或溴,较佳是氟及氯,尤以氟为佳。烷基及芳基基团可经部分卤化或是过卤化。甚至硝基,腈,酯,酰胺,亚磺酰基,磺酰基酰胺,及磺酰基可适用于做为烷基及芳基基团的取代基。芳基基团可经三氟-或是三氯甲基,以及铵基团所取代。适当的烷基R5实例包括:三氟甲基,三氯甲基,二氟甲基,2,2,2-三氟乙基,2,2,2-三氯乙基,3,3,3-三氟丙基,五氟乙基,硝基甲基,2-硝基甲基,2-硝基乙基及氰基甲基。其中以三氟甲基及2,2,2-三氟乙基为佳。适当的芳基R5实例是对-,间-,邻-氟或氯苯基,2,4-二氟苯基,2,4-二氯苯基,2,4,6-三氟苯基,五氟苯基,2,4,6-三氯苯基,硝基苯基,2,4-二硝基苯基,2-氯-5-硝基苯基,2-溴-5-硝基苯基,甲基亚磺酰基苯基及甲基磺酰基苯基。
本发明也提供催化剂组合物,其中包括钯(II)化合物及如通式R1R2P-CH2-N(R5)-CH2-PR3R4之二膦化合物,其中R1至R5如上述意义及较佳的意义。较佳的实施方案中,本发明之催化剂组合物中,一边的R1及R2,和在另一方的R3及R4相互连接,且独立是1,3-及/或1,4-亚环辛基,且R5是2,4-二氟苯基,五氟苯基或是2,4,6-三氟苯基。
钯(II)化合物参考本文开头所述。催化剂组合物中可包括阴离子来源,或是与阴离子来源共用。当钯(II)化合物是适当酸的钯盐,该酸可同时做为阴离子来源。
该二膦化合物也叫作二(膦基甲基)胺。其某些代表性制造法如J.Fawcett,P.A.T.Hoye et al.在J.Chem.Soc.DaltonTrans.1993,2563-2567中所述。
部分的双(膦基甲基)胺是新的。因此,本发明还提供如下通式结构的二膦化合物。
R1R2P-CH2-N(R5)-CH2-PR3R4
其中R1至R5如上述意义及较佳的意义,条件是,排除下列化合物,其中R1,R2,R3,及R4分别是苯基,且R5是CHMePh,CHMeCO2Me,CHMeCO2Et,内-(1R)-1,7,7-三甲基双环[2,2,1]庚-2-基,CH2CH2OH或是CH2CH=CH2;R1,R2,R3,及R4分别是环己基,R5是CHMePh或CHMeCO2H;或在一边的R1和R2及在另一方的R3及R4共为亚环辛基,且R5是CHMePh。(Me是甲基,Et是乙基,且Ph是苯基)。
例如,根据下述的一般反应流程可制造双(膦基甲基)胺:
所方便选择的反应条件可与J.Fawcett,P.A.T.Hoye,etal.,J.Chem.Soc.Dalton Trans.1993,2563-2567相类似。因此,双(膦基甲基)胺易于在一次反应中制备完成,其将二级膦与甲醛及氨或是伯胺反应,如,于溶剂中,例甲苯中,较佳的,于80℃-150℃中反应。
以钯为基准,二膦化合物对钯(II)化合物的摩尔比较佳是由0.5-20∶1,特别是由1至5∶1。
有效的阴离子包括路易士及质子酸,及其混合物。较佳的,所使用的阴离子来源是弱有机酸,如,具有pKa值为3.5或更高的有机酸,特别是具有空间位阻的有机酸。较佳的有机酸实例如,苯甲酸,2,4,6-三甲基苯甲酸,2,6-二氯苯甲酸,9-蒽羧酸,三甲基乙基酸,1,2,3-苯三羧酸及其部分酯,2-乙氧基-1-萘羧酸,2,6-二甲氧基苯甲酸,醋酸,丙酸,丁酸及/或氰戊酸。
其也可使用强无机酸,如,硫酸,过氯酸及强有机酸,如磺酸,例如,甲磺酸,对-甲苯磺酸,及苯磺酸,以及三氯-及三氟乙酸。
阴离子源对钯(II)化合物的摩耳比并不重要。较佳的,阴离子源对钯(II)化合物的摩耳比是由0.5-100∶1,特别是1-10∶1,相当于每摩耳的钯。
以使用氰戊酸为特佳,因为其中的有机酸阴离子来源与羟基化合物,如醇之酯副产物并不会对所得的反应产物造成污染。
本发明方法中所使用的羟基化合物可以是,如,水或醇,特别是具有1-6个碳原子的醇。所使用的醇可以是一级,二级或是三级醇。较佳的醇的实例包括,甲醇,乙醇,丙醇,异丙醇,丁醇类,正-己醇,正-辛醇,异辛醇,2-乙基已醇,环己醇,苯甲基醇,苯基乙基醇,乙二醇,1,2-丙二醇,1,3-丙二醇,新戊二醇,三甲醇丙烷及季戊四醇。其中以使用甲醇及乙醇为佳。
较佳的,将本发明方法于40-200℃下进行,特别是75-170℃。较佳的,将本发明方法于1-200bar压力下进行,特别是5-70bar。该反应可以批次,连续式或是半连续式的条件下进行。该反应时间通常是0.5-10小时。
根据本发明所使用的催化剂系统可以是均质化或是非均质化的。该催化剂系统也可以是固定化方式使用。合适的载体实例如,离子交换剂,在此情况下,例如在二膦化合物上的离子基团,如,上述定义在R5上的某些取代基Q,可与离子交换剂上的离子基团发生反应。藉著添加催化剂系统的溶液至离子交换剂中可使固定化发生,使得该催化剂系统被固定。
较佳的,使本发明方法于液相中进行。该液相可利用所使用的戊烯腈或是藉著所使用的羟基化合物生成。另外,液相中可包括溶剂。可使用任何惰性溶剂。该实例包括亚砜及砜,如,二甲基亚砜,二异丙砜,或是四氢噻吩,2,2-二氧化物,2-甲基环丁砜,3-甲基环丁砜,2-甲基-4-丁基环丁砜;芳烃,如,苯,甲苯,二甲苯;酯,如乙酸甲酯及丁内酯;酮,如,丙酮或甲基异丁基酮;醇,如,甲醇及乙醇,醚,如四氢呋喃,茴香醚,2,5,8-三氧壬烷,二苯基醚及二异丙基醚;酰胺,如二甲基乙酰胺及N-甲基吡咯烷酮。
较佳的,本发明方法应于基本上不含氧的状态下进行。因此,该反应器中,例如,应重复使呈真空,并以保护气体充填,如,氮气。在没有空气的情况下加入反应物、溶剂及催化剂系统。
本发明方法可以例如以如下方式进行:将2-戊烯腈,3-戊烯腈,4-戊烯腈,或其混合物,羟基化合物,催化剂系统,如本实例,及溶剂加入抗压反应器中。接着,注入一氧化碳及将反应器加热至所需的反应温度。若有需要,藉著打入一氧化碳或释出一氧化碳调整反应压力。当反应完成后,使混合物冷却,并解压缩。利用传统的方法可以将氰戊酸或其酯由混合物中分离出,例如,以分馏方式。
所使用的催化剂系统可依反应条件于原处生成。或是,较佳的,于先前即将催化剂系统先加以制备。为此,例如钯(II)化合物,二齿二膦配位体及,若需要的话,其阴离子来源均可溶解或是悬浮在相互溶解的溶剂中,并将该溶液或悬浮液混合。将钯(II)二膦络合物分离,如,以过滤法,若有需要可于添加降低溶解度的稀释剂后进行。
下述实例将可阐释本发明。
实例1
将28毫克(0.125mmol)的乙酸钯(II),155毫克(0.5mmol)的1,3-双(1,5-亚环辛基膦基)乙烷及1,2-双(1,4-亚环辛基膦基)乙烷混合物,及与1,5-及1,4-亚环辛基团之混合化合物(bcope),445毫克(2.0mmol)的9-蒽羧酸及3毫升(31mmol)的3-戊烯腈溶于10毫升的二苯基醚及5毫升的甲醇中,将其加至100毫升高压釜中。将高压釜密封,并打入一氧化碳至压力是40bar。将高压釜加热至150℃,并将总压力调整至60bar。根据表1的反应时间,使高压釜冷却将反应停止。将高压釜解压缩,并以气相层析分析液态流出物。
实例2
以下述的反应物及量使实例1于300毫升的高压釜中重覆进行:112毫克(0.5mmol)的乙酸钯(II),845毫克的(2.0mmol)1,2-双(二环已基膦基)乙烷,2.2克(10mmol)的9-蒽羧酸,12毫升(124mmol)的3-戊烯腈,20毫升的甲醇及40毫升的二苯基醚。
实例3
以下述的反应物及量将实例1重覆进行;28毫克(0.125mmol)的乙酸钯(II),116毫克的(0.375mmol)bcope,445毫克(2.0mmol)的9-蒽羧酸,10毫升(103mmol)的3-戊烯腈,15毫升的甲醇。
实例4
本实例的钯(II)二膦络合物系事先制备。
将1.0克(4.4mmol)的乙酸钯(II)先溶于50毫升的丙酮中,并于室温下将溶液搅拌2小时,以Celite过滤。将滤液与溶于50毫升丙酮中之2.1克(4.4mmol)的bcope悬浮液相混合,并于室温下搅拌1小时。将所得的白黄固体(bcope)Pd(OAc)2过滤去除,并使减压干燥。产率:2.2克(94%)。
将下述的反应物以陈述的量根据实例1重覆进行:67毫克(0.125mmol)的(bcope)Pd(OAc)2,445毫克(2.0mmol)的蒽羧酸,10毫升(103mmol)的3-戊烯腈及15毫升的甲醇。每项案例中的结果如下表所列。
实例 | 反应时间 | 3-PN的转换率 | TON | TOF | Sel.(CVE) | Sel.(5-CVE) |
1 | 6h | 90% | 192 | 32 | 90% | 70% |
2 | 15h | 40% | 85 | 14 | 90% | 71% |
3 | 3h | 57% | 470 | 157 | 90% | 72% |
4 | 3h | 62% | 494 | 165 | 90% | 72% |
CVE=氰戊酸酯
TON=转换数
TOF=转换频率
将实例4与实例3比较后显示使用经预制备,定义的(bcope)Pd(OAc)2络合物可改进催化剂活性。使用经预制备,定义的络合物的另一项优点是不需过量的二膦化合物。
实例5
本实例阐释了下述混合物的制备,1,3-双(1,4-亚环辛基膦基甲基)苯胺,1,3-双(1,5-亚环辛基膦基甲基)苯胺,1-(1,4-亚环辛基膦基甲基)-3-(1,5-亚环辛基膦基甲基)苯胺。
将1.2克(0.035mol)的多聚甲醛溶于100毫升的甲苯中,并将该悬浮液加热至65℃,再添加1.6毫升(0.0175mol)苯胺,及5克(0.035mol)的1,4-环辛烯基膦及1,5-环辛烯基膦的混合物。5h后可得澄清溶液后,使其冷却并使浓缩。将所得的残余溶于50毫升的二氯甲烷中,并以乙醇将螯合物膦沉淀。过滤后,减压使白色残余干燥。产率:4.8克(68%)。
实例6
本实例阐释下述物的制备:
1,3-双(1,4-亚环辛基膦基甲基)(2,4-二氟苯基)-胺,1,3-双(1,5-亚环辛基膦基甲基)(2,4-二氟苯基)-胺,1-(1,4-亚环辛基膦基甲基)-3-(1,5-亚环辛基膦基甲基)(2,4-二氟苯基)-胺(aza-bcope)。
将1.2克(0.035mol)的多聚甲醛溶于100毫升的甲苯中,并将该悬浮液加热至65℃。再添加1.8毫升(0.0175mol)2,4-二氟苯胺,及5克(0.035mol)的1,4-环辛烯基膦及1,5-环辛烯基膦的混合物,并将该溶液于65℃中搅拌过夜。冷却后使溶剂减压抽气,将所得的残余溶于20毫升的二氯甲烷中,并以醚使产物沉淀。将白色固体过滤后使减压干燥。产率:5.4克(70%)。
实例7
本实例阐释下述络合物混合物的制备:
1,3-双(1,4-亚环辛基膦基甲基)(2,4-二氟苯基)-胺-Pd(OAc)2,
1,3-双(1,5-亚环辛基膦基甲基)(2,4-二氟苯基)-胺-Pd(OAc)2,及
1-(1,4-亚环辛基膦基甲基)-3-(1,5-亚环辛基膦基甲基)(2,4-二氟苯基)-胺-Pd(OAc)2。
将0.45克(2.0mmol)的乙酸钯(II)溶于50毫升的丙酮中,于室温中搅拌2小时,并以Celite过滤。将滤液与溶于50毫升丙酮中之0.88克(2.2mmol)aza-bcope悬浮液相混合,并于室温中搅拌1小时。将所得的白黄色固体过滤出来后使减压干燥。产率:1.1克(88%)。
实例8
本实例说明以(aza-bcope)Pd(OAc)2络合物对3-戊烯腈进行羰基化反应。以下述的量之反应物利用实例1方法重覆进行:79毫克(0.125mmol)的(aza-bcope)Pd(OAc)2(参见实例7),445毫克(2.0mmol)的蒽羧酸,10毫升(103mmol)的3-戊烯腈及15毫升甲醇。
实例 | 反应时间 | 3-PN的转换率 | TON | TOF | Sel.(CVE) | Sel.(5-CVE) |
8 | 3h | 75% | 598 | 200 | 90% | 71% |
将实例8与实例4相比较可显示(aza-bcope)Pd(OAc)2催化剂系统明显具有较高的催化剂活性。
Claims (8)
1.一种制造氰戊酸或其酯的方法,将2-,3-,或4-戊烯腈或其混合物于催化剂系抗存在下,与一氧化碳及羟基化合物反应,该催化剂系统包括:
(i)钯(II)化合物,
(ii)二齿二膦配位体,其中的二膦配位体的通式如下:
R1R2P-X-PR3R4
其中的R1,R2,R3及R4独立地是C1-C20-烷基,C3-C10-环烷基,或芳基,C7-C20-芳烷基,其各自未经取代或经卤素原子,烷氧基,卤烷基,卤烷氧基,酰基基团,酰基氧基基团,氨基基团,羟基,腈基,酰基氨基或芳基取代,或是R1及R2及/或R3及R4共为C2-C20-亚烷基或亚芳基或是C7-C20-亚芳烷基,其各自未经取代或经卤素原子,烷氧基,卤烷基,卤烷氧基,酰基基团,酰基氧基基团,氨基基团,羟基,腈基,酰基氨基或芳基取代,且X是二价的桥键基团,其使得两翼的磷原子经1-10个原子分隔,及
(iii)阴离子来源。
2.根据权利要求1的方法,其中的R1,R2,R3及R4分别独立地是具有1-10个碳原子之未经取代、直链或具支链、直链或环烷基基团,或是R1及R2及/或R3及R4共为具有1-10个碳原子的直链或具支链、直链或环状亚烷基基团。
3.根据权利要求2的方法,其中的R1,R2,R3及R4系分别选自甲基,乙基,丙基,异丙基,正丁基,仲丁基,叔丁基及/或环己基基团,或是R1及R2及/或R3及R4共为五亚甲基、六亚甲基或是亚环辛基基团。
4.根据权利要求1至3项中任一项的方法,其中的X是可包括杂原子的亚烷基链。
5.根据权利要求4的方法,其中的X是
-CH2-N(R5)-CH2-
其中R5是氢,C1-C20-烷基,未经取代或是经C1-C6-烷基取代之C3-C10-环烷基,未经取代或是经C1-C6-烷基取代之C6-C20-芳基,未经取代或是经C1-C6-烷基取代之C7-C20-芳烷基,C2-C21-酰基,前述基团未经取代或经选自下列的取代基所取代:-MO,-NO2,-CN,-CO2 -,-CO2R6,-CONR6 2,卤素,-NR6 2,-OR6,-NR6+ 3,-SO3 -,-SO3R6,-SO2R6,SO2NR6 2,及SiR7 3,及/或前述基团中的1,2,3或4个碳原子可由N或O所取代,或是R5是硝基,腈,亚磺酰基,磺酰基或SiR7 3,R6是氢,C1-C10-烷基或C6-C14-芳基且R7是C1-C10-烷基或C6-C14-芳基。
6.根据权利要求1至3中任何一项的方法,其中的阴离子来源是pXa值为3.5或更高的有机酸。
7.一种如下通式的二膦化合物:
R1R2P-CH2-N(R5)-CH2-PR3R4,其中的R1,R2,R3及R4独立地是C1-C20-烷基,C3-C10-环烷基,或是芳基,C7-C20-芳烷基,其各自未经取代或经卤素原子,烷氧基,卤烷基,卤烷氧基,酰基基团,酰基氧基基团,氨基基团,羟基,腈基,酰基氨基或芳基取代,或是R1及R2及/或R3及R4共为C2-C20-亚烷基,或亚芳基或是C7-C20-亚芳烷基,其各自未经取代或经卤素原子,烷氧基,卤烷基,卤烷氧基,酰基基团,酰基氧基基团,氨基基团,羟基,腈基,酰基氨基或芳基取代,并且R5是氢,C1-C20-烷基,未经取代或是经C1-C6-烷基取代之C3-C10-环烷基,未经取代或是经C1-C6-烷基取代之C6-C20-芳基,未经取代或是经C1-C6-烷基取代之C7-C20-芳烷基,C2-C21-酰基,R5未经取代或经选自下列的取代基所取代:-NO,-NO2,-CN,-CO2 -,-CO2R6,-CONR6 2,卤素,-NR6 2,-OR6,-NR6+ 3,-SO3 -,-SO3R6,-SO2R6,SO2NR6 2,及SiR7 3,及/或前述基团中的1,2,3或4个碳原子可由N或O所取代,或是R5是硝基,腈,亚磺酰基,磺酰基或SiR7 3,R6是氢,C1-C10-烷基或C6-C14-芳基且R7是C1-C10-烷基或C6-C14-芳基,条件是:排除下列化合物,其中R1,R2,R3及R4分别是苯基,且R5是CHMePh,CHMeCO2Me,CHMeCO2Rt,内-(1R)-1,7,7-三甲基双环[2,2,1]庚-2-基,CH2CH2OH或CH2CH=CH2;R1,R2,R3及R4分别是环己基且R5是CHMePh或CHMeCO2H;或是在一方的R1及R2,以及在另一方的R3及R4共为亚环辛基,且R5是CHMePh。
8.一种催化剂组合物,其中包含钯(II)化合物及如下通式之二膦化合物:
R1R2P-CH2-N(R5)-CH2-pR3R4
其中的R1,R2,R3及R4独立地是C1-C20-烷基,C3-C10-环烷基,或是芳基,C7-C20-芳烷基,其各自未经取代或经卤素原子,烷氧基,卤烷基,卤烷氧基,酰基基团,酰基氧基基团,氨基基团,羟基,腈基,酰基氨基或芳基取代,或是R1及R2及/或R3及R4共为C2-C20-亚烷基,或亚芳基或是C7-C20-亚芳烷基,其各自未经取代或经卤素原子,烷氧基,卤烷基,卤烷氧基,酰基基团,酰基氧基基团,氨基基团,羟基,腈基,酰基氨基或芳基取代,并且R5是氢,C1-C20-烷基,未经取代或是经C1-C6-烷基取代之C3-C10-环烷基,未经取代或是经C1-C6-烷基取代之C6-C20-芳基,未经取代或是经C1-C6-烷基取代之C7-C20-芳烷基,C2-C21-酰基,R5未经取代或经选自下列的取代基所取代:-NO,-NO2,-CN,-CO2 -,-CO2R6,-CONR6 2,卤素,-NR6 2,-OR6,-NR6+ 3,-SO3 -,-SO3R6,-SO2R6,SO2NR6 2,及SiR7 3,及/或前述基团中的1,2,3或4个碳原子可由N或O所取代,或是R5是硝基,腈,亚磺酰基,磺酰基或SiR7 3,R6是氢,C1-C10-烷基或C6-C14-芳基且R7是C1-C10-烷基或C6-C14-芳基。
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DE19840253A DE19840253A1 (de) | 1998-09-03 | 1998-09-03 | Verfahren zur Herstellung von Cyanvaleriansäure oder -estern |
DE19840253.8 | 1998-09-03 |
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US6743911B2 (en) * | 2000-03-14 | 2004-06-01 | Shell Oil Company | Process for the carbonylation of pentenenitrile |
MY127358A (en) | 2000-03-14 | 2006-11-30 | Shell Int Research | Process for the carbonylation of ethylenically unsaturated compounds |
MY127093A (en) | 2000-05-17 | 2006-11-30 | Lucite Int Uk Ltd | Bidentate ligands useful in catalyst systems |
DE10060313A1 (de) | 2000-12-04 | 2002-06-13 | Basf Ag | Verfahren zur Carbonylierung von Pentensäure und deren Derivate |
DE10106348A1 (de) * | 2001-02-09 | 2002-08-14 | Basf Ag | Als Katalysator oder zur Herstellung eines Katalysatorsystems geeignete Verbindung |
EP1444241B1 (en) | 2001-11-09 | 2005-10-05 | Shell Internationale Researchmaatschappij B.V. | Bidendate ligands for the carbonylation of unsaturated compounds |
US20030105348A1 (en) * | 2001-11-19 | 2003-06-05 | Bunel Emilio E. | Process for making 5-cyanovaleric acid, adipic acid or dimethyl adipate |
US6806391B2 (en) * | 2002-07-31 | 2004-10-19 | Shell Oil Company | Process for the carbonylation of ethylenically unsaturated compounds and bidentate diphosphine composition used in this process |
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US3496215A (en) | 1965-11-23 | 1970-02-17 | Du Pont | Hydrocyanation of olefins using selected nickel phosphite catalysts |
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US4257973A (en) * | 1971-11-05 | 1981-03-24 | E. I. Du Pont De Nemours And Company | Process of making acids or esters from unsaturated compounds |
GB1429169A (en) | 1972-09-07 | 1976-03-24 | Ici Ltd | Manufacture of organic nitriles |
GB1497046A (en) | 1975-06-06 | 1978-01-05 | Ici Ltd | Cyano-substituted aliphatic carboxylic esters |
DE2541640C2 (de) | 1975-09-18 | 1983-12-08 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Herstellung von 5-Cyanvaleriansäure bzw. ihren Estern |
US4508660A (en) | 1983-03-14 | 1985-04-02 | E. I. Du Pont De Nemours And Company | Carbonylation of olefinically unsaturated nitriles and acids using a sulfone solvent |
GB8531624D0 (en) * | 1985-12-23 | 1986-02-05 | Shell Int Research | Carbonylation of ethylenically unsaturated compounds |
US4950778A (en) | 1988-12-12 | 1990-08-21 | E. I. Du Pont De Nemours & Company | Manufacture of 5-cyanovaleric acid and its esters using cyclic cosolvents |
US4933483A (en) | 1988-12-12 | 1990-06-12 | E. I. Du Pont De Nemours And Company | Manufacture of 5-cyanovaleric acid and its esters |
US5077425A (en) | 1990-04-02 | 1991-12-31 | E. I. Du Pont De Nemours And Company | Nitrile-accelerated hydrocarboxylation |
ES2088082T3 (es) | 1991-01-15 | 1996-08-01 | Shell Int Research | Carbonilacion de olefinas. |
US5670700A (en) | 1995-08-25 | 1997-09-23 | E. I. Du Pont De Nemours And Company | Hydroformylation process |
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TW524794B (en) | 2003-03-21 |
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BR9913404A (pt) | 2001-05-22 |
KR100589565B1 (ko) | 2006-06-14 |
WO2000014055A3 (de) | 2002-10-03 |
US6346640B1 (en) | 2002-02-12 |
EP1107947A2 (de) | 2001-06-20 |
AR020375A1 (es) | 2002-05-08 |
ID28203A (id) | 2001-05-10 |
JP2003519618A (ja) | 2003-06-24 |
WO2000014055A2 (de) | 2000-03-16 |
EP1107947B1 (de) | 2003-01-08 |
CA2342170A1 (en) | 2000-03-16 |
AU5858999A (en) | 2000-03-27 |
DE59903982D1 (de) | 2003-02-13 |
ES2191457T3 (es) | 2003-09-01 |
DE19840253A1 (de) | 2000-03-09 |
KR20010073091A (ko) | 2001-07-31 |
CN1429201A (zh) | 2003-07-09 |
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