TWI388545B - A method for preparing a catalytic composition of amide and a method for producing amide - Google Patents
A method for preparing a catalytic composition of amide and a method for producing amide Download PDFInfo
- Publication number
- TWI388545B TWI388545B TW098133115A TW98133115A TWI388545B TW I388545 B TWI388545 B TW I388545B TW 098133115 A TW098133115 A TW 098133115A TW 98133115 A TW98133115 A TW 98133115A TW I388545 B TWI388545 B TW I388545B
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- acid
- ionic liquid
- sulfate
- amino acid
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 23
- 239000000203 mixture Substances 0.000 title claims description 23
- 230000003197 catalytic effect Effects 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title description 7
- 150000001408 amides Chemical class 0.000 title description 2
- 125000003368 amide group Chemical group 0.000 title 1
- 239000002608 ionic liquid Substances 0.000 claims description 97
- 238000006243 chemical reaction Methods 0.000 claims description 48
- -1 hexafluorophosphate Chemical compound 0.000 claims description 48
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 38
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 37
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 claims description 37
- 239000002253 acid Substances 0.000 claims description 34
- 235000001014 amino acid Nutrition 0.000 claims description 34
- 229940024606 amino acid Drugs 0.000 claims description 34
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 31
- 150000001413 amino acids Chemical class 0.000 claims description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 16
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 15
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims description 15
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 14
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 14
- 125000003277 amino group Chemical group 0.000 claims description 13
- 150000001450 anions Chemical class 0.000 claims description 13
- 230000017105 transposition Effects 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 125000004414 alkyl thio group Chemical group 0.000 claims description 12
- 150000001768 cations Chemical class 0.000 claims description 12
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 12
- 125000004185 ester group Chemical group 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- IFMKHZCRZNMPJL-WCCKRBBISA-N (2s)-2-(dimethylamino)butanedioic acid;sulfuric acid Chemical compound OS(O)(=O)=O.CN(C)[C@H](C(O)=O)CC(O)=O IFMKHZCRZNMPJL-WCCKRBBISA-N 0.000 claims description 6
- FQEGIMDQLWZQNJ-FHAQVOQBSA-N (2s,3s)-2-amino-3-methylpentanoic acid;sulfuric acid Chemical compound OS(O)(=O)=O.CC[C@H](C)[C@H](N)C(O)=O FQEGIMDQLWZQNJ-FHAQVOQBSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 125000000879 imine group Chemical group 0.000 claims description 6
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 6
- YYECZHKRNLAODV-DFWYDOINSA-N (2s)-2-(methylamino)butanedioic acid;sulfuric acid Chemical compound OS(O)(=O)=O.CN[C@H](C(O)=O)CC(O)=O YYECZHKRNLAODV-DFWYDOINSA-N 0.000 claims description 5
- 239000007848 Bronsted acid Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 4
- 239000004475 Arginine Substances 0.000 claims description 4
- 125000001313 C5-C10 heteroaryl group Chemical group 0.000 claims description 4
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 4
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004473 Threonine Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 4
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 claims description 4
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 239000004472 Lysine Substances 0.000 claims description 3
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 3
- CIQHWLTYGMYQQR-QMMMGPOBSA-N O(4')-sulfo-L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(OS(O)(=O)=O)C=C1 CIQHWLTYGMYQQR-QMMMGPOBSA-N 0.000 claims description 3
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- KLRWOUZEYNJFEP-QRPNPIFTSA-N (2s)-2-amino-3-phenylpropanoic acid;sulfuric acid Chemical compound OS(O)(=O)=O.OC(=O)[C@@H](N)CC1=CC=CC=C1 KLRWOUZEYNJFEP-QRPNPIFTSA-N 0.000 claims description 2
- JHNRZXQVBKRYKN-VQHVLOKHSA-N (ne)-n-(1-phenylethylidene)hydroxylamine Chemical compound O\N=C(/C)C1=CC=CC=C1 JHNRZXQVBKRYKN-VQHVLOKHSA-N 0.000 claims description 2
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 claims description 2
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims description 2
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 claims description 2
- DNYZBFWKVMKMRM-UHFFFAOYSA-N n-benzhydrylidenehydroxylamine Chemical compound C=1C=CC=CC=1C(=NO)C1=CC=CC=C1 DNYZBFWKVMKMRM-UHFFFAOYSA-N 0.000 claims description 2
- SCRFXJBEIINMIC-UHFFFAOYSA-N n-cyclododecylidenehydroxylamine Chemical compound ON=C1CCCCCCCCCCC1 SCRFXJBEIINMIC-UHFFFAOYSA-N 0.000 claims description 2
- OENGSNXUALAIFP-UHFFFAOYSA-N n-cycloheptylidenehydroxylamine Chemical compound ON=C1CCCCCC1 OENGSNXUALAIFP-UHFFFAOYSA-N 0.000 claims description 2
- YGNXYFLJZILPEK-UHFFFAOYSA-N n-cyclopentylidenehydroxylamine Chemical compound ON=C1CCCC1 YGNXYFLJZILPEK-UHFFFAOYSA-N 0.000 claims description 2
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims 2
- SSGPUMSCFGYUSA-RGMNGODLSA-N S(=O)(=O)(O)O.CN([C@@H](CCSC)C(=O)O)C Chemical compound S(=O)(=O)(O)O.CN([C@@H](CCSC)C(=O)O)C SSGPUMSCFGYUSA-RGMNGODLSA-N 0.000 claims 2
- 235000003704 aspartic acid Nutrition 0.000 claims 2
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims 2
- MSZSGKIGWIVVOP-UHFFFAOYSA-N carboxymethylazanium;hydrogen sulfate Chemical compound NCC(O)=O.OS(O)(=O)=O MSZSGKIGWIVVOP-UHFFFAOYSA-N 0.000 claims 2
- PXVDJNMARHINII-WCCKRBBISA-N (2s)-pyrrolidine-2-carboxylic acid;sulfuric acid Chemical compound OS(O)(=O)=O.OC(=O)[C@@H]1CCCN1 PXVDJNMARHINII-WCCKRBBISA-N 0.000 claims 1
- WZKSXHQDXQKIQJ-UHFFFAOYSA-N F[C](F)F Chemical compound F[C](F)F WZKSXHQDXQKIQJ-UHFFFAOYSA-N 0.000 claims 1
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 claims 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 claims 1
- OKDITRZIFCHFGA-JEDNCBNOSA-N S(=O)(=O)(O)O.CN1[C@@H](CCC1)C(=O)O Chemical class S(=O)(=O)(O)O.CN1[C@@H](CCC1)C(=O)O OKDITRZIFCHFGA-JEDNCBNOSA-N 0.000 claims 1
- YUENFNPLGJCNRB-UHFFFAOYSA-N anthracen-1-amine Chemical group C1=CC=C2C=C3C(N)=CC=CC3=CC2=C1 YUENFNPLGJCNRB-UHFFFAOYSA-N 0.000 claims 1
- 238000005649 metathesis reaction Methods 0.000 claims 1
- KTPUHSVFNHULJH-UHFFFAOYSA-N n-cyclooctylidenehydroxylamine Chemical compound ON=C1CCCCCCC1 KTPUHSVFNHULJH-UHFFFAOYSA-N 0.000 claims 1
- IKVDMBQGHZVMRN-UHFFFAOYSA-N n-methyldecan-1-amine Chemical compound CCCCCCCCCCNC IKVDMBQGHZVMRN-UHFFFAOYSA-N 0.000 claims 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 16
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 5
- 239000004220 glutamic acid Substances 0.000 description 5
- 235000013922 glutamic acid Nutrition 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- OSQDRNJFQGNHBH-WCCKRBBISA-N (2s)-2-(methylamino)pentanedioic acid;sulfuric acid Chemical compound OS(O)(=O)=O.CN[C@H](C(O)=O)CCC(O)=O OSQDRNJFQGNHBH-WCCKRBBISA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- NQDCBEPBLOQJFY-JEDNCBNOSA-N (2s)-2-(dimethylamino)pentanedioic acid;sulfuric acid Chemical compound OS(O)(=O)=O.CN(C)[C@H](C(O)=O)CCC(O)=O NQDCBEPBLOQJFY-JEDNCBNOSA-N 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000006462 rearrangement reaction Methods 0.000 description 3
- VCXSWLXWTJZWGQ-DKWTVANSSA-N (2s)-2-aminobutanedioic acid;sulfuric acid Chemical compound OS(O)(=O)=O.OC(=O)[C@@H](N)CC(O)=O VCXSWLXWTJZWGQ-DKWTVANSSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- 239000011831 acidic ionic liquid Substances 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000007522 mineralic acids Chemical group 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000007524 organic acids Chemical group 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- AXWJKQDGIVWVEW-BYPYZUCNSA-N (2s)-2-(dimethylamino)butanedioic acid Chemical compound CN(C)[C@H](C(O)=O)CC(O)=O AXWJKQDGIVWVEW-BYPYZUCNSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- IHWDSEPNZDYMNF-UHFFFAOYSA-N 1H-indol-2-amine Chemical compound C1=CC=C2NC(N)=CC2=C1 IHWDSEPNZDYMNF-UHFFFAOYSA-N 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- HOKKHZGPKSLGJE-GSVOUGTGSA-N N-Methyl-D-aspartic acid Chemical compound CN[C@@H](C(O)=O)CC(O)=O HOKKHZGPKSLGJE-GSVOUGTGSA-N 0.000 description 1
- XLBVNMSMFQMKEY-BYPYZUCNSA-N N-methyl-L-glutamic acid Chemical compound CN[C@H](C(O)=O)CCC(O)=O XLBVNMSMFQMKEY-BYPYZUCNSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical group OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- HIGZEFHDFAMPND-UHFFFAOYSA-N azepan-2-one;sulfuric acid Chemical compound OS(O)(=O)=O.O=C1CCCCCN1 HIGZEFHDFAMPND-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229930195712 glutamate Natural products 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- DSLBDAPZIGYINM-UHFFFAOYSA-N sulfanium;chloride Chemical group S.Cl DSLBDAPZIGYINM-UHFFFAOYSA-N 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
-
- 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
- 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
- B01J31/0201—Oxygen-containing compounds
-
- 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
- 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
- B01J31/0201—Oxygen-containing compounds
- B01J31/0202—Alcohols or phenols
-
- 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
- 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
- B01J31/0201—Oxygen-containing compounds
- B01J31/0209—Esters of carboxylic or carbonic acids
-
- 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
- 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
- B01J31/0215—Sulfur-containing compounds
- B01J31/0217—Mercaptans or thiols
-
- 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
- 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
- B01J31/0215—Sulfur-containing compounds
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Description
本發明係關於一種用於製備醯胺之催化組成物及製備醯胺的方法，尤係有關於一種在離子液體以及布忍斯特酸之催化組成物存在下催化酮肟而製備醯胺。
己內醯胺是製造尼龍6纖維和薄膜的重要原料。環己酮肟的貝克曼轉位反應是生產己內醯胺最重要的反應步驟，目前傳統重排反應過程係以發煙硫酸(Oleum)作為催化劑，將環己酮肟經液相貝克曼轉位反應為己內醯胺硫酸鹽，然後再以氨水中和而得到己內醯胺。雖然整個反應環己酮肟的轉化率幾乎為100%，己內醯胺的選擇率為99%，但整個反應不僅產生大量低價值的硫酸銨，而且催化的濃硫酸對整個設備所引起的腐蝕、環境污染等問題。近年來研發新的己內醯胺生產技術方向均著重在減少或避免副產物硫酸銨的生成。其次，與氣相反應相比，液相轉位反應具有反應條件溫和、對設備要求不高等優點，有利於現有設備的改造。是以，國內外學者發展液相轉位反應的研究，並取得相當發展與突破。例如，日本住友公司於第1852898A號中國專利利用具有磺酸根官能基的離子液體作為反應催化劑，使己內醯胺的選擇率達99%，中國科學院蘭州化學物理研究所於第1919834號中國專利以具有磺醯氯官能基的離子液體為催化劑，使己內醯胺的選擇率達97.2%，荷蘭DSM公司於WO2008/145312A1專利以硫酸根為陰離子的離子液體進行轉位反應，使醯胺的選擇率為99%。
然而，上述專利僅使用酸性離子液體以催化進行轉位反應，在轉位反應後的產物己內醯胺與離子液體產生化學鍵結時，若無法及時有效分離產物，便使得轉位反應後的離子液體黏度大為提高，因而造成管線堵塞，不利於製程商業化。
因此，亟需一種有效降低離子液體黏度又具有高酮肟轉化率與醯胺選擇率之催化組成物，用以催化酮肟製備醯胺。
鑑此，本發明係提供一種用於製備醯胺之催化組成物，包括：具有下式(I)之陽離子和包括一種或多種無機酸根、有機酸根或其所構成之組群的陰離子的胺基酸離子液體，
式(I)中，R1
為氫、環狀亞胺基、或C1-8
烷基，其中，該C1-8
烷基係未經取代或經羥基(-OH)、羧基(-COOH)、胍基(NH2
C(=NH)NH-)、胺基(-NH2
)、醯胺基(-CONH2
)、酯基(-COOR，其中，R為C1-8
烷基)、磺酸基(-SO3
H)、氯亞磺醯基(ClSO-)、羥基苯基、C1-8
烷硫基、巰基(-SH)、C6-10
芳基或5至10員雜芳基之取代基取代；R2
及R3
各獨立地為氫或C1-8
烷基，其中，該C1-8
烷基係未經取代或經羥基(-OH)、羧基(-COOH)、胍基(NH2
C(=NH)NH-)、胺基(-NH2
)、醯胺基(-CONH2
)、酯基(-COOR)、磺酸基(-SO3
H)、氯亞磺醯基(ClSO-)、側氧基(=O)、羥基苯基、C1-8
烷硫基、巰基(-SH)、C6-10
芳基或5至10員雜芳基之取代基取代；其中，該陽離子與陰離子之數目為能使該胺基酸離子液體成為電中性者；以及布忍斯特(Bronsted)酸。
本發明亦提供一種製備醯胺之方法，包括：在具有下式(I)之陽離子和包括一種或多種無機酸根、有機酸根或其所構成之組群的陰離子的胺基酸離子液體，及布忍斯特酸之存在下，催化酮肟之貝克曼轉位反應以生成醯胺。
式(I)中，R1
為氫、環狀亞胺基、或C1-8
烷基，其中，該C1-8
烷基係未經取代或經羥基(-OH)、羧基(-COOH)、胍基(NH2
C(=NH)NH-)、胺基(-NH2
)、醯胺基(-CONH2
)、酯基(-COOR，其中，R為C1-8
烷基)、磺酸基(-SO3
H)、氯亞磺醯基(ClSO-)、羥基苯基、C1-8
烷硫基、巰基(-SH)、C6-10
芳基或5至10員雜芳基之取代基取代。
R2
及R3
各獨立地為氫或C1-8
烷基，其中，該C1-8
烷基係未經取代或經羥基(-OH)、羧基(-COOH)、胍基(NH2
C(=NH)NH-)、胺基(-NH2
)、醯胺基(-CONH2
)、酯基(-COOR)、磺酸基(-SO3
H)、氯亞磺醯基(ClSO-)、側氧基(=O)、羥基苯基、C1-8
烷硫基、巰基(-SH)、C6-10
芳基或5至10員雜芳基之取代基取代。其中，該陽離子與陰離子之數目為能使該胺基酸離子液體成為電中性者。
相較於僅使用酸性離子液體作為反應催化組成物以製備醯胺的方法，本發明方法係使用離子液體以及布忍斯特酸作為催化組成物以製備醯胺，具有降低離子液體黏度與提升反應活性之優點，亦有高酮肟重排反應轉化率及醯胺選擇率，適合工業化大規模生產。
以下係藉由特定的具體實施例說明本發明之實施方式，熟習此技藝之人士可由本說明書所揭示之內容輕易地瞭解本發明之優點及功效。本發明亦可藉由其它不同之實施方式加以施行或應用，本說明書中的各項細節亦可基於不同觀點與應用，在不悖離本發明所揭示之精神下賦予不同之修飾與變更。
本發明係提供一種用於製備醯胺之催化組成物，包括具有下式(I)之陽離子和包括一種或多種無機酸根、有機酸根或其所構成之組群的陰離子的胺基酸離子液體：
式(I)中，R1
為氫、環狀亞胺基或C1-8
烷基，其中，該C1-8
烷基係未經取代或經羥基(-OH)、羧基(-COOH)、胍基(NH2
C(=NH)NH-)、胺基(-NH2
)、醯胺基(-CONH2
)、酯基(-COOR，其中，R為C1-8
烷基)、磺酸基(-SO3
H)、氯亞磺醯基(ClSO-)、羥基苯基、C1-8
烷硫基、巰基(-SH)、C6-10
芳基或5至10員雜芳基之取代基取代；R2
及R3
各獨立地為氫或C1-8
烷基，其中，該C1-8
烷基係未經取代或經羥基(-OH)、羧基(-COOH)、胍基(NH2
C(=NH)NH-)、胺基(-NH2
)、醯胺基(-CONH2
)、酯基(-COOR)、磺酸基(-SO3
H)、氯亞磺醯基(ClSO-)、側氧基(=O)、羥基苯基、C1-8
烷硫基、巰基(-SH)、C6-10
芳基或5至10員雜芳基之取代基取代；以及布忍斯特(Bronsted)酸。
於一具體實施例中，R1
為經羧基(-COOH)、胍基(NH2
C(=NH)NH-)、胺基(-NH2
)、醯胺基(-CONH2
)或羥基苯基取代之C1-8
烷基，且該R2
與R3
獨立地為C1-8
烷基。
在本文中，「C1-8
烷基」係指直鏈狀、分枝鏈狀或環狀烷基，該C1-8
烷基的實例包括，但非限於甲基、乙基、丙基、異丙基、丁基、第二丁基、戊基、己基及環己基，其中，以甲基、乙基、丙基、丁基及戊基為較佳。
本發明之較佳具體實例中，該胺基酸離子液體係甘胺酸硫酸型離子液體、異白胺酸硫酸型離子液體、精胺酸硫酸型離子液體、穀胺酸硫酸型離子液體、酪胺酸硫酸型離子液體、天冬胺酸硫酸型離子液體、離胺酸硫酸型離子液體、蘇胺酸硫酸型離子液體、苯丙胺酸硫酸型離子液體、絲胺酸硫酸型離子液體或其所構成組群之胺基酸硫酸型離子液體。較佳地，本發明之胺基酸型離子液體以N,N-二甲基穀胺酸硫酸鹽、N,N-二甲基天冬胺酸硫酸鹽、N-甲基穀胺酸硫酸鹽及N-甲基天冬胺酸硫酸鹽為較佳。此外，於本發明之方法中，可使用一種或多種的胺基酸離子液體，具體而言，於一較佳實施例中，該胺基酸離子液體係N,N-二甲基天冬胺酸硫酸鹽、N-甲基穀胺酸硫酸鹽、N-甲基天冬胺酸硫酸鹽、N,N-二甲基穀胺酸硫酸鹽或其所構成組群者，亦即可選擇為N,N-二甲基天冬胺酸硫酸鹽及N-甲基穀胺酸硫酸鹽的組合或N,N-二甲基天冬胺酸硫酸鹽、N-甲基穀胺酸硫酸鹽及N-甲基天冬胺酸硫酸鹽的組合。
本發明之催化組成物中，該陰離子係一種或多種硫酸根、甲基磺酸根、三氟醋酸根、六氟磷酸根、氟硼酸根或其組成群組者。其中，以硫酸根為較佳。
一般而言，該胺基酸離子液體與布忍斯特酸之莫耳比係介於1:10至10:1之範圍內，較佳係介於1:5至5:1之範圍內，更佳係介於2:1至1:2之範圍內。
本發明亦提供一種製備醯胺之方法，包括在具有下式(I)之陽離子和包括一種或多種無機酸根、有機酸根或其所構成之組群的陰離子的胺基酸離子液體，及布忍斯特酸之存在下，催化酮肟之貝克曼轉位反應以生成醯胺：
式(I)中，R1
為氫、環狀亞胺基或C1-8
烷基，其中，該C1-8
烷基係未經取代或經羥基(-OH)、羧基(-COOH)、胍基(NH2
C(=NH)NH-)、胺基(-NH2
)、醯胺基(-CONH2
)、酯基(-COOR，其中，R為C1-8
烷基)、磺酸基(-SO3
H)、氯亞磺醯基(ClSO-)、羥基苯基、C1-8
烷硫基、巰基(-SH)、C6-10
芳基或5至10員雜芳基之取代基取代；R2
及R3
各獨立地為氫或C1-8
烷基，其中，該C1-8
烷基係未經取代或經羥基(-OH)、羧基(-COOH)、胍基(NH2
C(=NH)NH-)、胺基(-NH2
)、醯胺基(-CONH2
)、酯基(-COOR)、磺酸基(-SO3
H)、氯亞磺醯基(ClSO-)、側氧基(=O)、羥基苯基、C1-8
烷硫基、巰基(-SH)、C6-10
芳基或5至10員雜芳基之取代基取代。其中，該陽離子與陰離子之數目為能使該胺基酸離子液體成為電中性者。
於一較佳具體實施例中，R1
為經羧基(-COOH)、胍基(NH2
C(=NH)NH-)、胺基(-NH2
)、醯胺基(-CONH2
)或羥基苯基取代之C1-8
烷基，且該R2
與R3
獨立地為C1-8
烷基。
本發明之製備醯胺方法中，該陰離子包括一種或多種硫酸根、甲基磺酸根、三氟醋酸根、六氟磷酸根、氟硼酸根或其組成群組者。於本發明之一具體實例中，該陰離子為硫酸根。
在本發明中，並未特別限制布忍斯特酸的種類，通常，該布忍斯特酸包括，但不限於硫酸、磷酸、醋酸、甲基磺酸、三氟甲基磺酸、三氟醋酸、六氟磷酸或氟硼酸。此外，亦可選用單一酸或混合酸，是以，本發明之布忍斯特酸係選自硫酸、磷酸、醋酸、甲基磺酸、三氟甲基磺酸、三氟醋酸、六氟磷酸、氟硼酸及其組合所組成群組之一者或多者。在本發明之一較佳具體實施例中，該布忍斯特酸為硫酸。
一般而言，在本發明之方法實施例中，該胺基酸離子液體與布忍斯特酸之莫耳比係介於1:10至10:1之範圍內，較佳係介於1:5至5:1之範圍內，更佳係介於2:1至1:2之範圍內。
此外，該胺基酸離子液體和布忍斯特酸之莫耳總和與該酮肟之莫耳的比係介於1:10至10:1之範圍內，較佳係介於1:5至5:1之範圍內，更佳係介於3:1至1:3之範圍內。於本發明之製備醯胺實例中，酮肟的轉換率幾乎為100%，己內醯胺的選擇率可達98.8%。是以，在本發明之催化組成物存在下，催化酮肟經貝克曼轉位反應以生成醯胺具有優異的反應活性。
本發明之製備醯胺方法中，反應溫度為60至150℃，較佳為80至130℃，最佳為90至120℃，且反應滯留時間為0.1至10小時，較佳為0.25至4小時，最佳為0.5至1小時。
在本發明之一具體實施例中，該酮肟為環己酮肟。但本發明用於製備醯胺時所用之酮肟係包括丙酮肟、丁酮肟、二苯甲酮肟、苯乙酮肟、環戊酮肟、環己酮肟、環庚酮肟、環辛酮肟或環十二酮肟之化合物。
本發明之方法中，該胺基酸離子液體係甘胺酸硫酸型離子液體、異白胺酸硫酸型離子液體、精胺酸硫酸型離子液體、穀胺酸硫酸型離子液體、酪胺酸硫酸型離子液體、天冬胺酸硫酸型離子液體、離胺酸硫酸型離子液體、蘇胺酸硫酸型離子液體、苯丙胺酸硫酸型離子液體、絲胺酸硫酸型離子液體或其所組成之群組。較佳地，本發明之胺基酸離子液體以異白胺酸硫酸型離子液體、N,N-二甲基穀胺酸硫酸鹽、N,N-二甲基天冬胺酸硫酸鹽、N-甲基穀胺酸硫酸鹽及N-甲基天冬胺酸硫酸鹽為較佳。在本發明之一具體實施例中，該胺基酸離子液體係穀胺酸硫酸型離子液體。此外，亦可使用一種或多種的胺基酸離子液體。
以下係藉由特定之具體實施例進一步說明本發明之特點與功效，但非用於限制本發明之範疇。
本發明之實施例如下所示，但本發明並不限於這些實施例。酮肟及醯胺係由氣相層析法分析，且酮肟的轉換率和醯胺的選擇率係由下列方程式計算：
轉換率(%)=[經反應的酮肟莫耳數/原始的酮肟莫耳數(%)]×100%
選擇率(%)=[所得的醯胺莫耳數/經反應的酮肟莫耳數]×100%
實施例1至5係根據表1所載內容，於250ml的三頸圓底燒瓶中加入N,N-二甲基穀胺酸硫酸型離子液體0.01mole與硫酸0.01mole作為反應催化組成物，再添加甲苯溶劑50ml，以磁石攪拌並升溫至110℃後，再加入指定量的酮肟，其中，離子液體和布忍斯特酸之莫耳總和與酮肟之莫耳的比係依序為5/1至5/5，反應進行0.5小時後，以氣相層析儀測定反應物的轉化率與產物的選擇率，並將結果紀錄於下表1。
實施例6至10中，係根據表2所載內容，於250ml的三頸圓底燒瓶中加入0.01mole穀胺酸硫酸型離子液體與指定量之硫酸作為反應催化組成物，再添加甲苯溶劑50ml，以磁石攪拌並升溫至110℃後，再加入酮肟，其中，離子液體和布忍斯特酸之莫耳總和與酮肟之莫耳的比係5/2，反應進行0.5小時後，以氣相層析儀測定反應物的轉化率與產物的選擇率，並將結果紀錄於下表2。
比較例1至5中，係根據表3所載內容，於250ml的三頸圓底燒瓶中僅加入穀胺酸硫酸型離子液體0.01mole作為反應催化組成物，再添加甲苯溶劑50ml，以磁石攪拌並升溫至110℃後，再加入指定量的酮肟，其中，離子液體與酮肟之莫耳比係依序為5/1至5/5，反應進行0.5小時後，以氣相層析儀測定反應物的轉化率與產物的選擇率，並將結果紀錄於下表。
由上述結果顯示，本發明在以穀胺酸硫酸型離子液體以及硫酸作為反應催化組成物，用以催化酮肟而製備醯胺時，具有高酮肟轉化率與醯胺選擇率，其中，當離子液體和布忍斯特酸/酮肟的莫耳比在5/2至5/3之間時，具有較佳的轉化率和選擇率。此外，在本發明催化組成物存在下，得以增加酮肟之用量而不需擔心轉化率或選擇率不佳之問題，具有利於提升產量之優點。
分別使用實施例3及比較例3於反應前與反應後所用之反應催化組成物，在60℃下以黏度計量測其黏度變化並將實驗結果紀錄於下表4。
由上述結果顯示，本發明利用離子液體以及布忍斯特酸作為反應催化組成物，在液相轉位反應條件下催化酮肟而製備醯胺，可降低反應後離子液體的黏度與提升反應催化活性。此外，較佳的反應溫度和反應時間為100至110℃和0.5至1小時之間。
本發明之反應催化系統簡單，不需再添加其他的助催化劑，可在反應後降低離子液體黏度、提升反應活性和提高酮肟重排反應轉化率及醯胺選擇率，且無副產物生成，不會造成環境污染而且節約能源，適合工業化大規模生產，具有良好的工業應用前景。
上述實施例僅例示性說明本發明之原理及其功效，而非用於限制本發明。任何熟習此項技藝之人士均可'在不違背本發明之精神及範疇下，對上述實施例進行修飾與改變。因此，本發明之權利保護範圍，應如後述之申請專利範圍所列。
本案無圖式。
Claims (18)
- 一種用於製備醯胺之催化組成物，包括：具有式(I)之陽離子和包括一種或多種硫酸根、甲基磺酸根、三氟醋酸根、六氟磷酸根、氟硼酸根或其所組成群組的陰離子的胺基酸離子液體，
- 如申請專利範圍第1項之催化組成物，其中，該胺基酸離子液體與布忍斯特酸之莫耳比係介於1：10至10：1。
- 如申請專利範圍第2項之催化組成物，其中，該胺基酸離子液體和布忍斯特酸之莫耳比係介於1：5至5：1。
- 如申請專利範圍第2項之催化組成物，其中，該R1 為經羧基(-COOH)、胍基(NH2 C(=NH)NH-)、胺基(-NH2 )、醯胺基(-CONH2 )或羥基苯基取代之C1-8 烷基，且該R2 與R3 獨立地為C1-8 烷基。
- 如申請專利範圍第4項之催化組成物，其中，該胺基酸離子液體係甘胺酸硫酸型離子液體、異白胺酸硫酸型離子液體、精胺酸硫酸型離子液體、榖胺酸硫酸型離子液體、酪胺酸硫酸型離子液體、天冬胺酸硫酸型離子液體、離胺酸硫酸型離子液體、蘇胺酸硫酸型離子液體、苯丙胺酸硫酸型離子液體、絲胺酸硫酸型離子液體或其所構成組群之胺基酸硫酸型離子液體。
- 如申請專利範圍第5項之催化組成物，其中，該胺基酸離子液體係異白胺酸硫酸型離子液體、N,N-二甲基天冬胺酸硫酸鹽、N-甲基榖胺酸硫酸鹽、N-甲基天冬胺酸硫酸鹽、N,N-二甲基榖胺酸硫酸鹽或其所構成組群者。
- 一種製備醯胺之方法，包括：在具有式(I)之陽離子和包括一種或多種硫酸根、甲基磺酸根、三氟醋酸根、六氟磷酸根、氟硼酸根或其所組成群組的陰離子的胺基酸 離子液體，及布忍斯特酸之存在下，催化酮肟之貝克曼轉位反應以生成醯胺，
- 如申請專利範圍第7項之方法，其中，該R1 為經羧基(-COOH)、胍基(NH2 C(=NH)NH-)、胺基(-NH2 )、醯胺基 (-CONH2 )或羥基苯基取代之C1-8 烷基，且該R2 與R3 獨立地為C1-8 烷基。
- 如申請專利範圍第8項之方法，其中，該胺基酸離子液體係甘胺酸硫酸型離子液體、異白胺酸硫酸型離子液體、精胺酸硫酸型離子液體、榖胺酸硫酸型離子液體、酪胺酸硫酸型離子液體、天冬胺酸硫酸型離子液體、離胺酸硫酸型離子液體、蘇胺酸硫酸型離子液體、苯丙胺酸硫酸型離子液體、絲胺酸硫酸型離子液體或其所構成組群之胺基酸硫酸型離子液體。
- 如申請專利範圍第9項之方法，其中，該胺基酸離子液體係異白胺酸硫酸型離子液體、N,N-二甲基天冬胺酸硫酸鹽、N-甲基榖胺酸硫酸鹽、N-甲基天冬胺酸硫酸鹽、N,N-二甲基榖胺酸硫酸鹽或其所構成組群者。
- 如申請專利範圍第7項之方法，其中，該胺基酸離子液體與布忍斯特酸之莫耳比係介於1：10至10：1。
- 如申請專利範圍第11項之方法，其中，該胺基酸離子液體與布忍斯特酸之莫耳比係介於1：5至5：1。
- 如申請專利範圍第11項之方法，其中，該胺基酸離子液體和布忍斯特酸之莫耳總和與該酮肟之莫耳比係介於1：10至10：1。
- 如申請專利範圍第13項之方法，其中，該胺基酸離子液體和布忍斯特酸之莫耳總和與該酮肟之莫耳比係介於1：5至5：1。
- 如申請專利範圍第7或13項之方法，其中，該酮肟係 丙酮肟、丁酮肟、二苯甲酮肟、苯乙酮肟、環戊酮肟、環己酮肟、環庚酮肟、環辛酮肟或環十二酮肟。
- 如申請專利範圍第7或13項之方法，該貝克曼轉位反應係於60至150℃進行。
- 如申請專利範圍第16項之方法，該貝克曼轉位反應係於80至130℃進行。
- 如申請專利範圍第7項之方法，該貝克曼轉位反應時間為0.1至10小時。
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| US12/627,681 US8367865B2 (en) | 2009-09-30 | 2009-11-30 | Method and catalyst composition for preparing amide |
| JP2010216977A JP5106607B2 (ja) | 2009-09-30 | 2010-09-28 | アミドの製造に用いられる触媒組成物及びアミドの製造方法 |
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| CN105017117A (zh) * | 2015-07-08 | 2015-11-04 | 南京工业大学 | 一种微反应装置中试放大生产己内酰胺的方法 |
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