CN108355709B - Application of bismuth trifluoromethanesulfonate as Beckmann rearrangement reaction catalyst - Google Patents
Application of bismuth trifluoromethanesulfonate as Beckmann rearrangement reaction catalyst Download PDFInfo
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- CN108355709B CN108355709B CN201810141850.1A CN201810141850A CN108355709B CN 108355709 B CN108355709 B CN 108355709B CN 201810141850 A CN201810141850 A CN 201810141850A CN 108355709 B CN108355709 B CN 108355709B
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- oxime
- reaction
- ketoxime
- beckmann rearrangement
- acetonitrile
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- HIYUMYXSGIKHHE-UHFFFAOYSA-M bismuth trifluoromethanesulfonate Chemical compound [Bi+3].[O-]S(=O)(=O)C(F)(F)F HIYUMYXSGIKHHE-UHFFFAOYSA-M 0.000 title claims abstract description 54
- 238000006237 Beckmann rearrangement reaction Methods 0.000 title claims abstract description 37
- 239000007809 chemical reaction catalyst Substances 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 116
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 180
- 239000002904 solvent Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 13
- 150000001408 amides Chemical class 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- DNYZBFWKVMKMRM-UHFFFAOYSA-N n-benzhydrylidenehydroxylamine Chemical compound C=1C=CC=CC=1C(=NO)C1=CC=CC=C1 DNYZBFWKVMKMRM-UHFFFAOYSA-N 0.000 claims description 8
- NYENCOMLZDQKNH-UHFFFAOYSA-K bis(trifluoromethylsulfonyloxy)bismuthanyl trifluoromethanesulfonate Chemical compound [Bi+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F NYENCOMLZDQKNH-UHFFFAOYSA-K 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 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 6
- XXOHMWCSTKXDLH-YFHOEESVSA-N (nz)-n-[1-(4-methoxyphenyl)ethylidene]hydroxylamine Chemical compound COC1=CC=C(C(\C)=N/O)C=C1 XXOHMWCSTKXDLH-YFHOEESVSA-N 0.000 claims description 6
- XAAUYUMBCPRWED-NTMALXAHSA-N (nz)-n-[1-(4-methylphenyl)ethylidene]hydroxylamine Chemical compound O/N=C(/C)C1=CC=C(C)C=C1 XAAUYUMBCPRWED-NTMALXAHSA-N 0.000 claims description 6
- JYAQYXOVOHJRCS-UHFFFAOYSA-N 1-(3-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(Br)=C1 JYAQYXOVOHJRCS-UHFFFAOYSA-N 0.000 claims description 6
- BVZSQTRWIYKUSF-UHFFFAOYSA-N 4-(N-hydroxy-C-methylcarbonimidoyl)phenol Chemical compound ON=C(C)C1=CC=C(O)C=C1 BVZSQTRWIYKUSF-UHFFFAOYSA-N 0.000 claims description 6
- VSJKFVUSFMENIX-UHFFFAOYSA-N n-[1-(2-methylphenyl)ethylidene]hydroxylamine Chemical compound ON=C(C)C1=CC=CC=C1C VSJKFVUSFMENIX-UHFFFAOYSA-N 0.000 claims description 6
- -1 p-chlorophenyl-acetophenone oxime Chemical compound 0.000 claims description 6
- BAYUSCHCCGXLAY-UHFFFAOYSA-N 1-(3-methoxyphenyl)ethanone Chemical compound COC1=CC=CC(C(C)=O)=C1 BAYUSCHCCGXLAY-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- YPFOSEYKSLTSSF-UHFFFAOYSA-N n-[1-(4-fluorophenyl)ethylidene]hydroxylamine Chemical compound ON=C(C)C1=CC=C(F)C=C1 YPFOSEYKSLTSSF-UHFFFAOYSA-N 0.000 claims description 5
- GVDONFUHZNOGQH-UHFFFAOYSA-N n-[cyclohexyl(phenyl)methylidene]hydroxylamine Chemical compound C=1C=CC=CC=1C(=NO)C1CCCCC1 GVDONFUHZNOGQH-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- WPEOEYHUTFZJKZ-UHFFFAOYSA-N 3-(n-hydroxy-c-methylcarbonimidoyl)phenol Chemical compound ON=C(C)C1=CC=CC(O)=C1 WPEOEYHUTFZJKZ-UHFFFAOYSA-N 0.000 claims description 4
- MBKGQYQOTXYSRQ-UHFFFAOYSA-N n-[1-(2-chlorophenyl)ethylidene]hydroxylamine Chemical compound ON=C(C)C1=CC=CC=C1Cl MBKGQYQOTXYSRQ-UHFFFAOYSA-N 0.000 claims description 4
- KAXTWDXRCMICEQ-UHFFFAOYSA-N n-[1-(4-chlorophenyl)ethylidene]hydroxylamine Chemical compound ON=C(C)C1=CC=C(Cl)C=C1 KAXTWDXRCMICEQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000001544 thienyl group Chemical group 0.000 claims description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 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 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 125000002541 furyl group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- XMSZANIMCDLNKA-UHFFFAOYSA-N methyl hypofluorite Chemical compound COF XMSZANIMCDLNKA-UHFFFAOYSA-N 0.000 claims description 3
- OMZQGWSYEDCTKB-UHFFFAOYSA-N n-(1-thiophen-2-ylpropylidene)hydroxylamine Chemical compound CCC(=NO)C1=CC=CS1 OMZQGWSYEDCTKB-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- GMUHKJNYROUBTE-UHFFFAOYSA-N C1(CCCCC1)C1=C(C(C2=CC=CC=C2)=NO)C=CC=C1 Chemical compound C1(CCCCC1)C1=C(C(C2=CC=CC=C2)=NO)C=CC=C1 GMUHKJNYROUBTE-UHFFFAOYSA-N 0.000 claims 1
- NYFZDDJDWLLEQG-UHFFFAOYSA-N C1=CC=C(C=C1)C(=NO)CC2=CC=CS2 Chemical compound C1=CC=C(C=C1)C(=NO)CC2=CC=CS2 NYFZDDJDWLLEQG-UHFFFAOYSA-N 0.000 claims 1
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 238000007867 post-reaction treatment Methods 0.000 abstract description 3
- 238000006462 rearrangement reaction Methods 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 113
- 238000001035 drying Methods 0.000 description 66
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 38
- 238000003756 stirring Methods 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 238000002360 preparation method Methods 0.000 description 19
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 18
- 238000001914 filtration Methods 0.000 description 18
- 239000008188 pellet Substances 0.000 description 18
- 239000007832 Na2SO4 Substances 0.000 description 17
- 238000004440 column chromatography Methods 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 17
- 239000012074 organic phase Substances 0.000 description 17
- 229910052938 sodium sulfate Inorganic materials 0.000 description 17
- 238000005303 weighing Methods 0.000 description 15
- 239000000725 suspension Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- LUJMEECXHPYQOF-UHFFFAOYSA-N 3-hydroxyacetophenone Chemical compound CC(=O)C1=CC=CC(O)=C1 LUJMEECXHPYQOF-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- MVFAARYRSUJHJD-UHFFFAOYSA-N n-[bis(4-methylphenyl)methylidene]hydroxylamine Chemical compound C1=CC(C)=CC=C1C(=NO)C1=CC=C(C)C=C1 MVFAARYRSUJHJD-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- HCKGQAZSGFSOBM-UHFFFAOYSA-N n-[bis(4-fluorophenyl)methylidene]hydroxylamine Chemical compound C=1C=C(F)C=CC=1C(=NO)C1=CC=C(F)C=C1 HCKGQAZSGFSOBM-UHFFFAOYSA-N 0.000 description 2
- QTSWPNAWJHHXKG-UHFFFAOYSA-N n-[bis(4-methoxyphenyl)methylidene]hydroxylamine Chemical compound C1=CC(OC)=CC=C1C(=NO)C1=CC=C(OC)C=C1 QTSWPNAWJHHXKG-UHFFFAOYSA-N 0.000 description 2
- MRIYHLMTPKMDAJ-UHFFFAOYSA-N n-benzoyl-n-formylbenzamide Chemical compound C=1C=CC=CC=1C(=O)N(C=O)C(=O)C1=CC=CC=C1 MRIYHLMTPKMDAJ-UHFFFAOYSA-N 0.000 description 2
- ZHDORMMHAKXTPT-UHFFFAOYSA-N n-benzoylbenzamide Chemical compound C=1C=CC=CC=1C(=O)NC(=O)C1=CC=CC=C1 ZHDORMMHAKXTPT-UHFFFAOYSA-N 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- DCPLOIFDMMEBQZ-UHFFFAOYSA-N 2-bromo-n-phenylacetamide Chemical compound BrCC(=O)NC1=CC=CC=C1 DCPLOIFDMMEBQZ-UHFFFAOYSA-N 0.000 description 1
- PJFNNMFXEVADGK-UHFFFAOYSA-N 2-hydroxy-n-phenylacetamide Chemical compound OCC(=O)NC1=CC=CC=C1 PJFNNMFXEVADGK-UHFFFAOYSA-N 0.000 description 1
- LEQAQBFYCMENLP-UHFFFAOYSA-N 2-methoxy-n-phenylacetamide Chemical compound COCC(=O)NC1=CC=CC=C1 LEQAQBFYCMENLP-UHFFFAOYSA-N 0.000 description 1
- BPEXTIMJLDWDTL-UHFFFAOYSA-N 2`-Methylacetanilide Chemical compound CC(=O)NC1=CC=CC=C1C BPEXTIMJLDWDTL-UHFFFAOYSA-N 0.000 description 1
- YICAMJWHIUMFDI-UHFFFAOYSA-N 4-acetamidotoluene Chemical compound CC(=O)NC1=CC=C(C)C=C1 YICAMJWHIUMFDI-UHFFFAOYSA-N 0.000 description 1
- GGUOCFNAWIODMF-UHFFFAOYSA-N 4-chloroacetanilide Chemical compound CC(=O)NC1=CC=C(Cl)C=C1 GGUOCFNAWIODMF-UHFFFAOYSA-N 0.000 description 1
- NJOOHWMFLNMYGF-UHFFFAOYSA-N N-[1-(4-chlorophenyl)-2-hydroxyiminoethylidene]hydroxylamine Chemical compound ON=CC(=NO)C1=CC=C(Cl)C=C1 NJOOHWMFLNMYGF-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- LXRZVMYMQHNYJB-UNXOBOICSA-N [(1R,2S,4R)-4-[[5-[4-[(1R)-7-chloro-1,2,3,4-tetrahydroisoquinolin-1-yl]-5-methylthiophene-2-carbonyl]pyrimidin-4-yl]amino]-2-hydroxycyclopentyl]methyl sulfamate Chemical compound CC1=C(C=C(S1)C(=O)C1=C(N[C@H]2C[C@H](O)[C@@H](COS(N)(=O)=O)C2)N=CN=C1)[C@@H]1NCCC2=C1C=C(Cl)C=C2 LXRZVMYMQHNYJB-UNXOBOICSA-N 0.000 description 1
- FZENGILVLUJGJX-UHFFFAOYSA-N acetaldehyde oxime Chemical compound CC=NO FZENGILVLUJGJX-UHFFFAOYSA-N 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- MTIGMGPOXRUUMD-UHFFFAOYSA-N n-[1-(4-fluorophenyl)propan-2-ylidene]hydroxylamine Chemical compound ON=C(C)CC1=CC=C(F)C=C1 MTIGMGPOXRUUMD-UHFFFAOYSA-N 0.000 description 1
- AZTGEJBZSFKULT-UHFFFAOYSA-N n-phenylcyclohexanecarboxamide Chemical compound C1CCCCC1C(=O)NC1=CC=CC=C1 AZTGEJBZSFKULT-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- KNVQTRVKSOEHPU-UHFFFAOYSA-N o-Chloroacetanilide Chemical compound CC(=O)NC1=CC=CC=C1Cl KNVQTRVKSOEHPU-UHFFFAOYSA-N 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- 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
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
- B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/30—Hetero atoms other than halogen
- C07D333/36—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of organic chemistry, and relates to application of bismuth trifluoromethanesulfonate as a catalyst for Beckmann rearrangement reaction. Bismuth trifluoromethanesulfonate is used as a catalyst in Beckmann rearrangement reaction, the reaction condition is mild, the conversion rate of ketoxime rearrangement reaction is high, the selectivity is good, the post-reaction treatment is simple, the operability is good in industry, and the bismuth trifluoromethanesulfonate is green and nontoxic, can be recycled and used, and saves resources.
Description
Technical Field
The invention belongs to the field of organic chemistry, relates to Beckmann rearrangement reaction, and more particularly relates to application of bismuth trifluoromethanesulfonate as a catalyst of the Beckmann rearrangement reaction, namely a method for preparing amide from ketoxime through the Beckmann rearrangement reaction by using the bismuth trifluoromethanesulfonate as the catalyst.
Background
Ketoxime compounds are rearranged into substituted amides under the action of an acidic catalyst, and the reaction is called Beckmann rearrangement reaction. The reaction is firstly discovered in 1886 by the German chemist Enster-Otto Beckmann (Ernst Otto Beckmann), the reaction mechanism is that under the action of acid, oxime is firstly protonated, then a molecule of water is removed, meanwhile, a group which is in a reverse position with a hydroxyl group is transferred to an electron-deficient nitrogen atom, and the formed carbocation is reacted with water to obtain amide. The beckmann rearrangement reaction plays an extremely important role in organic synthesis and is commonly used for determining the structure of ketone compounds. The beckmann rearrangement is a stereospecific reaction, a hydrocarbon group and a leaving group (hydroxyl group) which are migrated in a ketoxime molecule are in a contraposition with each other, and the configuration of a migrated carbon atom is kept unchanged in the migration process. Cyclohexanone oxime is industrially utilized to generate Beckmann rearrangement to produce caprolactam in large quantities, which is a monomer for synthesizing nylon-6. The good properties of amides, such as large polarity, stability and structural diversity, also make it one of the most common and most valued functional groups of all branches of organic chemistry.
Lewis acid (Lewis acid) -catalyzed organic reactions and their research in organic synthesis have been the hot spots of organic chemistry research. Lewis acid catalyzed organic reactions are widely used in various fields, including the synthesis of natural products, due to their high selectivity, high yield, and mild reaction conditions. Conventional lewis acids, for example: AlCl3、BF3、TiCl4、SnCl4And the like have been widely used in organic synthesis. However, the traditional Lewis acid catalyst has large dosage and is sensitive to water, and the catalyst can not be recycled and reused. Therefore, the method seeks a green catalyst with non-harsh operating conditions, realizes the Beckmann rearrangement reaction under mild and environment-friendly conditions, has high conversion rate, good selectivity, simple and convenient post-treatment and good operability, and is a common effort target of organic chemists.
Disclosure of Invention
Based on the above problems, the inventors of the present invention have made an effort to research beckmann rearrangement reaction, and found that bismuth trifluoromethanesulfonate is used as a catalyst in beckmann rearrangement reaction, and that the reaction conditions are mild, the conversion rate of ketoxime rearrangement reaction is high, the selectivity is good, the post-reaction treatment is simple, the operability is good in industry, and bismuth trifluoromethanesulfonate is green and nontoxic, and can be recycled and reused, thereby saving resources.
Accordingly, it is an object of the present invention to provide the use of bismuth triflate as a catalyst for beckmann rearrangement reactions.
The invention also aims to provide a method for preparing amide from ketoxime by Beckmann rearrangement reaction by using bismuth trifluoromethanesulfonate as a catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
according to one aspect of the invention, the invention provides the use of bismuth triflate as a catalyst for beckmann rearrangement.
According to another aspect of the present invention, there is provided a process for producing an amide, which comprises subjecting a ketoxime to a beckmann rearrangement reaction in the presence of bismuth trifluoromethanesulfonate as a catalyst to convert the ketoxime to an amide.
The present invention is described more specifically below.
Bismuth triflate acts as a catalyst in the beckmann rearrangement reaction. Bismuth triflate (Bi (OTf)3) Also called as bismuth trifluoromethanesulfonate and bismuth trifluoromethanesulfonate, has the advantages of no toxicity, environmental protection and low price.
In the invention, under the catalytic action of bismuth trifluoromethanesulfonate, ketoxime is subjected to Beckmann rearrangement reaction and converted into amide.
In the present invention, the bismuth trifluoromethanesulfonate is used in an amount of 10 to 20 mol%, preferably 15 to 20 mol%, and more preferably 15 mol% based on the ketoxime in the beckmann rearrangement reaction. Taking the Beckmann rearrangement reaction of the benzophenone oxime under the catalysis of the bismuth trifluoromethanesulfonate as an example (acetonitrile is used as a solvent, the reaction temperature is 80 ℃), when the amount of the catalyst is 10%, the yield of the dibenzoyl formamide is 82% after 2h of reaction; when the dosage of 15 percent and 20 percent is adopted, the effects of the two are not obviously different, and the yield of the dibenzoyl formamide is close to 100 percent after 2 hours of reaction. In view of economy and environmental protection, the catalyst is preferably selected to be used in an amount of 15%.
In the present invention, the ketoxime is not limited, and ketoximes that can be used in the beckmann rearrangement reaction in the prior art are all suitable for use in the present invention, and ketoximes represented by the following general formula are preferred:
wherein R is1And R2Each independently is: substituted or unsubstituted alkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted cycloalkyl. Further, the alkyl group may be a C1-C6 alkyl group, and preferably a C1-C3 alkyl group; the aryl group may be phenyl, thienyl, furyl or the like, and is preferably phenyl or thienyl; the cycloalkyl group may be cyclopentyl or cyclohexyl. The substituted means that the alkyl, aryl or cycloalkyl can be substituted by a substituent selected from methyl, methoxy, fluorine, chlorine, bromine, hydroxyl.
Still further, the ketoxime is most preferably selected from the group consisting of benzophenone oxime, 4 ' -dimethyl benzophenone oxime, 4 ' -dimethoxy benzophenone oxime, 4 ' -difluoro benzophenone oxime, acetophenone oxime, p-fluoro acetophenone oxime, p-chloro acetophenone oxime, p-hydroxy acetophenone oxime, p-methyl acetophenone oxime, p-methoxy acetophenone oxime, m-hydroxy acetophenone oxime, 3-bromo acetophenone oxime, 3-methoxy acetophenone oxime, o-methyl acetophenone oxime, o-chloro acetophenone oxime, cyclohexyl phenyl ketone oxime, and 2-thienyl ethyl ketone oxime, and the structural formulas are respectively as follows:
in the present invention, the reaction solvent is not limited, and any solvent that can be used in the beckmann rearrangement reaction in the prior art is suitable for the present invention, and is preferably acetonitrile, toluene or benzene, more preferably acetonitrile.
In the present invention, the temperature of the beckmann rearrangement reaction may be 50 to 100 ℃, and preferably 60 to 90 ℃, and more preferably, the reflux temperature is about 80 ℃. The reaction time is not limited, and may be 0.5 to 10 hours, preferably 0.5 to 6 hours, and more preferably 2 to 4 hours.
In the present invention, the ketoxime can be prepared by reacting the corresponding ketone with hydroxylamine hydrochloride, for example, in a mixed solvent of water and ethanol at a volume ratio of 1:5, in the presence of sodium hydroxide, the ketone reacts with hydroxylamine hydrochloride to obtain the ketoxime.
Advantageous effects
Compared with the traditional strong acid catalytic Beckmann rearrangement process, the method has the following advantages:
(1) selecting Bi (OTf)3As a catalyst for Beckmann rearrangement reaction, Bi (OTf)3Green, non-toxic and environment-friendly.
(2) The reaction system is simple, and other auxiliary catalysts are not required to be added;
(3) the reaction condition is mild, and the reaction is carried out under the conditions of normal pressure and 80 ℃;
(4) the ketoxime rearrangement reaction has high conversion rate and good selectivity;
(5) simple post-reaction treatment and better industrial operability
(6) The catalyst can be recycled and reused, and resources are saved.
Detailed Description
The present invention will be further described with reference to specific examples, which are provided for illustrative purposes only and are not intended to limit the scope of the present invention.
In the following examples, DCM stands for dichloromethane; d6-DMSO represents deuterated dimethyl sulfoxide.
Preparation of example 1
Synthesis of benzophenone oxime
In a 100mL round bottom flask, benzophenone (1.82g, 10mmol) and 37.5mL 99.7% ethanol were added. Adding hydroxylamine hydrochloride (1.74g, 25mmol), sodium hydroxide (0.60g, 15mmol) and 7.5mL of water into the round-bottom flask under stirring, controlling the ratio of water to ethanol to be 1:5 in the system, carrying out reflux condensation reaction at 90 ℃ for 5-6 hours, monitoring by TLC (ethyl acetate to petroleum ether to be 1:4), after the reaction is completed, spinning off the ethanol in the solvent, placing the solvent in an ice bath, adding ice water into the flask, separating out a large amount of white solid, and carrying out suction filtration to obtain white tiny granular benzophenone oxime crystals with the yield of 98%.
1H NMR(400MHz,d6-DMSO,ppm):11.34(s,1H),7.48-7.41(m,4H),7.39-7.35(m,4H),7.28(d,J＝8.0Hz,2H)；
13C NMR(101MHz,d6-DMSO,ppm):155.58,137.18,133.95,129.31,129.28,128.81,128.77,128.58,127.39；
IR (KBr pellet): vC＝N＝1491.7cm–1。
4,4 ' -dimethyl benzophenone oxime, 4 ' -dimethoxy benzophenone oxime, 4 ' -difluoro benzophenone oxime, acetophenone oxime, p-fluoro acetophenone oxime, p-chloro acetophenone oxime, p-hydroxy acetophenone oxime, p-methyl acetophenone oxime, p-methoxy acetophenone oxime, m-hydroxy acetophenone oxime, 3-bromo acetophenone oxime, 3-methoxy acetophenone oxime, o-methyl acetophenone oxime, o-chloro acetophenone oxime, cyclohexyl phenyl ketone oxime, 2-thienyl ethyl ketone oxime were prepared in the same manner as in preparation example 1.
EXAMPLE 1 preparation of Benzamide
Taking a 50mL reaction bottle, transferring benzophenone oxime (0.18g, 1mmol) dissolved in 2mL acetonitrile into the reaction bottle, adding bismuth trifluoromethanesulfonate (0.10g, 0.15mmol) dissolved in 1mL acetonitrile under the condition of stirring, finally adding 2-3mL acetonitrile, and stirring for reaction under the condition of 80 ℃ oil bath. After the mixture of benzophenone oxime and bismuth trifluoromethanesulfonate was stirred, the solution immediately appeared as a white suspension, and the reaction was monitored by TLC (DCM: 100%) until the reaction was complete and proceeded for about 2 hours. Stopping heating, spin-drying the solvent with a rotary evaporator, extracting with water and DCM, combining the organic phases, and extracting with anhydrous Na2SO4And (5) drying. Filtering, concentrating, and separating by column chromatography(DCM: 100%), spin-dried, suction-dried, the dry product weighed out and the yield calculated to be 98%.
mp 168-169℃；
1H NMR(400MHz,d6-DMSO,ppm):10.22(s,1H),7.93(d,J＝8.0Hz,2H),7.76(d,J＝8.0Hz,2H),7.57(t,J＝8.0Hz,1H),7.51(t,J＝8.0Hz,2H),7.33(t,J＝8.0Hz,2H),7.08(t,J＝8.0Hz,1H)；
13C NMR(101MHz,d6-DMSO,ppm):165.99,139.59,135.41,131.98,129.04,128.82,128.07,124.09,120.79；
IR (KBr pellet): vC＝O＝1667.1cm–1。
EXAMPLE 24 preparation of 4, 4' -Dimethylbenzamide
Taking a 50mL reaction bottle, transferring 4, 4' -dimethyl benzophenone oxime (0.23g, 1mmol) dissolved in 2mL acetonitrile into the reaction bottle, adding bismuth trifluoromethanesulfonate (0.10g, 0.15mmol) dissolved in 1mL acetonitrile under the condition of stirring, finally adding 2-3mL acetonitrile, and stirring for reaction under the condition of 80 ℃ oil bath. After 4, 4' -dimethylbenzophenone oxime and bismuth trifluoromethanesulfonate were mixed and stirred, the solution immediately appeared as a white suspension, and the reaction was monitored by TLC (DCM: 100%) until completion, and the reaction was allowed to proceed for about 4 hours. Stopping heating, spin-drying the solvent with a rotary evaporator, extracting with water and DCM, combining the organic phases, and extracting with anhydrous Na2SO4And (5) drying. Filtration, concentration, column chromatography (DCM: 100%), spin-drying, pump-drying, weighing of the dried product and calculation of the yield to 78%.
mp 165-170℃；
1H NMR(400MHz,d6-DMSO,ppm):10.05(s,1H),7.85(d,J＝8.0Hz,2H),7.64(d,J＝8.0Hz,2H),7.30(d,J＝8.0Hz,2H),7.12(d,J＝8.0Hz,2H),2.36(s,3H),2.25(s,3H)；
13C NMR(101MHz,d6-DMSO,ppm):165.55,141.83,137.15,132.88,132.58,129.38,129.29,128.06,120.80,21.43,20.93；
IR (KBr pellet): vC＝O＝1642.9cm–1。
EXAMPLE 34 preparation of 4, 4' -Dimethoxybenzamide
Taking a 50mL reaction bottle, transferring 4, 4' -dimethoxy benzophenone oxime (0.26g, 1mmol) dissolved in 2mL acetonitrile into the reaction bottle, adding bismuth trifluoromethanesulfonate (0.10g, 0.15mmol) dissolved in 1mL acetonitrile under the condition of stirring, finally adding 2-3mL acetonitrile, and stirring for reaction under the condition of 80 ℃ oil bath. After 4, 4' -dimethoxybenzophenone oxime and bismuth trifluoromethanesulfonate were mixed and stirred, the solution immediately appeared as a white suspension, and the reaction was monitored by TLC (DCM: 100%) until completion, and the reaction was allowed to proceed for about 4 hours. Stopping heating, spin-drying the solvent with a rotary evaporator, extracting with water and DCM, combining the organic phases, and extracting with anhydrous Na2SO4And (5) drying. Filtration, concentration, column chromatography (DCM: 100%), spin-drying, pump-drying, weighing of the dried product and calculation of the yield to 87%.
mp 207-209℃；
1H NMR(400MHz,d6-DMSO,ppm):9.93(s,1H),7.92(d,J＝8.0Hz,2H),7.63(d,J＝8.0Hz,2H),7.02(d,J＝8.0Hz,2H),6.89(d,J＝8.0Hz,2H),3.81(s,3H),3.72(s,3H)；
13C NMR(101MHz,d6-DMSO,ppm):164.84,162.16,155.81,132.82,129.86,127.49,122.37,114.11,113.98,55.84,55.59；
IR (KBr pellet): vC＝O＝1652.2cm–1。
EXAMPLE 44 preparation of 4, 4' -Difluorobenzamide
Taking a 50mL reaction bottle, dissolving 4, 4' -difluorobenzophenone oxime in 2mL acetonitrile(0.24g, 1mmol) was transferred to a reaction flask, and bismuth triflate (0.10g, 0.15mmol) dissolved in 1mL acetonitrile was added under stirring, and finally 2-3mL acetonitrile was added, and the reaction was stirred under an oil bath at 80 ℃. After 4, 4' -difluorobenzophenone oxime and bismuth trifluoromethanesulfonate were mixed and stirred, the solution immediately appeared as a pale yellow solution, and the reaction was monitored by TLC (DCM: 100%) until the reaction was complete, and the reaction was allowed to proceed for about 4 hours. Stopping heating, spin-drying the solvent with a rotary evaporator, extracting with water and DCM, combining the organic phases, and extracting with anhydrous Na2SO4And (5) drying. Filtration, concentration, column chromatography (DCM: 100%), spin-drying, pump-drying, weighing of the dried product and calculation of the yield to 84%.
mp 192-193℃；
1H NMR(400MHz,d6-DMSO,ppm):10.30(s,1H),8.03-7.99(m,2H),7.77-7.74(m,2H),7.35(t,J＝8.0Hz,2H),7.18(t,J＝8.0Hz,2H)；
13C NMR(101MHz,d6-DMSO,ppm):164.84,163.22,159.92,157.50,135.77,130.80(d,J＝9.09Hz,1C),122.65(d,J＝8.08Hz,1C),115.72(q,J＝37.37Hz,1C)；
IR (KBr pellet): vC＝O＝1652.2cm–1。
EXAMPLE 5 preparation of acetanilide
Taking a 50mL reaction bottle, transferring acetophenone oxime (0.12g, 1mmol) dissolved in 2mL acetonitrile into the reaction bottle, adding bismuth trifluoromethanesulfonate (0.10g, 0.15mmol) dissolved in 1mL acetonitrile under the condition of stirring, finally adding 2-3mL acetonitrile, and stirring for reaction under the condition of 80 ℃ oil bath. After the acetophenone oxime and bismuth trifluoromethanesulfonate were mixed and stirred, the solution immediately appeared as a colorless solution, and the reaction was monitored by TLC (DCM: 100%) until the reaction was completed, and the reaction was allowed to proceed for about 3 hours. Stopping heating, spin-drying the solvent with a rotary evaporator, extracting with water and DCM, combining the organic phases, and extracting with anhydrous Na2SO4And (5) drying. Filtering, concentrating, separating by column chromatography (DCM: 100%),spin dry, pump dry, weigh dry product and calculate yield to 89%.
mp 79-80℃；
1H NMR(400MHz,d6-DMSO,ppm):9.89(s,1H),7.55(d,J＝8.0Hz,2H),7.26(t,J＝8.0Hz,2H),7.00(t,J＝8.0Hz,1H),2.01(s,3H)；
13C NMR(101MHz,d6-DMSO,ppm):168.67,139.37,128.93,123.23,119.37,24.13；
IR (KBr pellet): vC＝O＝1670.7cm–1。
EXAMPLE 6 preparation of Parafluoroacetanilide
Taking a 50mL reaction bottle, transferring p-fluorophenylacetoxime (0.17g, 1mmol) dissolved in 2mL acetonitrile into the reaction bottle, adding bismuth trifluoromethanesulfonate (0.10g, 0.15mmol) dissolved in 1mL acetonitrile under the condition of stirring, finally adding 2-3mL acetonitrile, and stirring for reaction under the condition of 80 ℃ oil bath. After the mixture of the p-fluoroacetophenone oxime and bismuth trifluoromethanesulfonate was stirred, the solution immediately appeared to be a white suspension, and the reaction was monitored by TLC (DCM: 100%) until the reaction was complete and proceeded for about 4 hours. Stopping heating, spin-drying the solvent with a rotary evaporator, extracting with water and DCM, combining the organic phases, and extracting with anhydrous Na2SO4And (5) drying. Filtration, concentration, column chromatography (DCM: 100%), spin-drying, pump-drying, weighing of the dried product and calculation of the yield to 88%.
mp 157-157℃；
1H NMR(400MHz,d6-DMSO,ppm):9.94(s,1H),7.56(dd,J＝8.0Hz,2H),7.09(t,J＝8.0Hz,2H),2.00(s,3H)；
13C NMR(101MHz,d6-DMSO,ppm):168.56,159.45,156.37,136.08(d,J＝14.14Hz,1C),121.08(d,J＝8.08Hz,1C),115.60(d,J＝22.22Hz,1C),24.28；
IR (KBr pellet): vC＝O＝1662.9cm–1。
EXAMPLE 7 preparation of p-chloroacetanilide
Taking a 50mL reaction bottle, transferring p-chlorophenyl glyoxime (0.17g, 1mmol) dissolved in 2mL acetonitrile into the reaction bottle, adding bismuth trifluoromethanesulfonate (0.10g, 0.15mmol) dissolved in 1mL acetonitrile under the condition of stirring, finally adding 2-3mL acetonitrile, and stirring for reaction under the condition of 80 ℃ oil bath. After p-chloroacetophenone oxime and bismuth trifluoromethanesulfonate were mixed and stirred, the solution immediately appeared as a white suspension, and the reaction was monitored by TLC (DCM: 100%) until completion, and the reaction proceeded for about 5 hours. Stopping heating, spin-drying the solvent with a rotary evaporator, extracting with water and DCM, combining the organic phases, and extracting with anhydrous Na2SO4And (5) drying. Filtration, concentration, column chromatography (DCM: 100%), spin-drying, suction-drying, weighing of the dried product and calculation of the yield 80%.
mp 183-184℃；
1H NMR(400MHz,d6-DMSO,ppm):10.04(s,1H),7.59(d,J＝6.0Hz,2H),7.31(d,J＝8.0Hz,2H),2.02(s,3H)；
13C NMR(101MHz,d6-DMSO,ppm):168.86,138.70,128.99,126.91,120.88,24.42；
IR (KBr pellet): vC＝O＝1650.2cm–1。
EXAMPLE 8 preparation of p-hydroxyacetanilide
Taking a 50mL reaction bottle, transferring p-hydroxy acetophenone oxime (0.15g, 1mmol) dissolved in 2mL acetonitrile into the reaction bottle, adding bismuth trifluoromethanesulfonate (0.10g, 0.15mmol) dissolved in 1mL acetonitrile under the condition of stirring, finally adding 2-3mL acetonitrile, and stirring for reaction under the condition of 80 ℃ oil bath. After p-hydroxyacetophenone oxime and bismuth trifluoromethanesulfonate were mixed and stirred, the solution immediately appeared as a white suspension, which was monitored by TLC (DCM: MeOH ═ 3:1)The reaction was carried out for about 4 hours until the reaction was completed. Stopping heating, spin-drying the solvent with a rotary evaporator, extracting with water and DCM, combining the organic phases, and extracting with anhydrous Na2SO4And (5) drying. Filtration, concentration, column chromatography (DCM: MeOH ═ 3:1), spin-drying, pump-drying, weighing of the dried product and calculated yield 80%.
mp 130-135℃；
1H NMR(400MHz,d6-DMSO,ppm):9.63(s,1H),9.12(s,1H),7.31(d,J＝8.0Hz,2H),6.65(d,J＝8.0Hz,2H),1.95(s,3H)；
13C NMR(101MHz,d6-DMSO,ppm):167.53,153.12,131.05,120.81,115.00,23.77；
IR (KBr pellet): vC＝O＝1659.3cm–1。
EXAMPLE 9 preparation of p-methylacetanilide
Taking a 50mL reaction bottle, transferring p-methyl acetophenone oxime (0.15g, 1mmol) dissolved in 2mL acetonitrile into the reaction bottle, adding bismuth trifluoromethanesulfonate (0.10g, 0.15mmol) dissolved in 1mL acetonitrile under the condition of stirring, finally adding 2-3mL acetonitrile, and stirring for reaction under the condition of 80 ℃ oil bath. After the p-methylacetophenone oxime and bismuth trifluoromethanesulfonate were mixed and stirred, the solution immediately appeared to be a white suspension, and the reaction was monitored by TLC (DCM: 100%) until the reaction was complete and proceeded for about 3 hours. Stopping heating, spin-drying the solvent with a rotary evaporator, extracting with water and DCM, combining the organic phases, and extracting with anhydrous Na2SO4And (5) drying. Filtration, concentration, column chromatography (DCM: 100%), spin-drying, pump-drying, weighing of the dried product and calculation of the yield to 82%.
mp 153-154℃；
1H NMR(400MHz,d6-DMSO,ppm):7.55(s,1H),7.37(d,J＝8.0Hz,2H),7.10(d,J＝8.0Hz,2H),2.30(s,3H),2.14(s,3H)；
13C NMR(101MHz,d6-DMSO,ppm):168.52,135.39,133.94,129.45,120.14,24.46,20.87；
IR (KBr pellet): vC＝O＝1663.5cm–1。
EXAMPLE 10 preparation of Paracetanilide
Taking a 50mL reaction bottle, transferring p-methoxy acetophenone oxime (0.17g, 1mmol) dissolved in 2mL acetonitrile into the reaction bottle, adding bismuth trifluoromethanesulfonate (0.10g, 0.15mmol) dissolved in 1mL acetonitrile under the condition of stirring, finally adding 2-3mL acetonitrile, and stirring for reaction under the condition of 80 ℃ oil bath. After p-methoxy acetophenone oxime and bismuth trifluoromethanesulfonate were mixed and stirred, the solution immediately appeared as a pale yellow suspension, and the reaction was monitored by TLC (DCM: 100%) until completion, and the reaction proceeded for about 3 hours. Stopping heating, spin-drying the solvent with a rotary evaporator, extracting with water and DCM, combining the organic phases, and extracting with anhydrous Na2SO4And (5) drying. Filtration, concentration, column chromatography (DCM: 100%), spin-drying, pump-drying, weighing of the dried product and calculated yield of 91%.
mp 127-129℃；
1H NMR(400MHz,d6-DMSO,ppm):9.75(s,1H),7.45(d,J＝8.0Hz,2H),6.84(d,J＝8.0Hz,2H),3.69(s,3H),1.98(s,3H)；
13C NMR(101MHz,d6-DMSO,ppm):168.13,155.27,132.96,120.93,55.42,24.15；
IR (KBr pellet): vC＝O＝1652.2cm–1。
EXAMPLE 113 preparation of hydroxyacetanilide
Taking a 50mL reaction bottle, transferring 3-hydroxy acetophenone oxime (0.15g, 1mmol) dissolved in 2mL acetonitrile into the reaction bottle, adding the mixture dissolved in acetonitrile under stirring1mL of acetonitrile in bismuth triflate (0.10g, 0.15mmol), and finally 2-3mL of acetonitrile were added and the reaction was stirred in an oil bath at 80 ℃. After 3-hydroxyacetophenone oxime and bismuth trifluoromethanesulfonate were mixed and stirred, the solution immediately appeared as a white suspension, and the reaction was monitored by TLC (DCM: 100%) until completion, and the reaction was allowed to proceed for about 4 hours. Stopping heating, spin-drying the solvent with a rotary evaporator, extracting with water and DCM, combining the organic phases, and extracting with anhydrous Na2SO4And (5) drying. Filtration, concentration, column chromatography (DCM: 100%), spin-drying, suction-drying, weighing of the dried product and calculation of the yield, 68%.
mp 124-126℃；
1H NMR(400MHz,d6-DMSO,ppm):9.93(s,1H),9.40(s,1H),7.17(s,1H),7.01(t,J＝8.0Hz,1H),6.93(d,J＝8.0Hz,1H),6.43(s,1H),2.00(s,3H)；
13C NMR(101MHz,d6-DMSO,ppm):168.85,158.04,140.85,129.69,110.65,110.32,106.73,24.54；
IR (KBr pellet): vC＝O＝1685.8cm–1。
EXAMPLE 123 preparation of Bromoacetanilide
Taking a 50mL reaction bottle, transferring 3-bromoacetophenone oxime (0.21g, 1mmol) dissolved in 2mL acetonitrile into the reaction bottle, adding bismuth trifluoromethanesulfonate (0.10g, 0.15mmol) dissolved in 1mL acetonitrile under the condition of stirring, finally adding 2-3mL acetonitrile, and stirring for reaction under the condition of 80 ℃ oil bath. After 3-bromoacetophenone oxime and bismuth trifluoromethanesulfonate were mixed and stirred, the solution immediately appeared as a slightly white suspension, and the reaction was monitored by TLC (DCM: 100%) until completion, and the reaction proceeded for about 4 hours. Stopping heating, spin-drying the solvent with a rotary evaporator, extracting with water and DCM, combining the organic phases, and extracting with anhydrous Na2SO4And (5) drying. Filtration, concentration, column chromatography (DCM: 100%), spin-drying, pump-drying, weighing of the dried product and calculation of the yield to 60%.
mp 86-88℃；
1H NMR(400MHz,d6-DMSO,ppm):10.08(s,1H),7.93(s,1H),7.44(d,J＝8.0Hz,1H),7.25-7.18(m,2H),2.03(s,3H)；
13C NMR(101MHz,d6-DMSO,ppm):169.10,141.32,131.13,126.01,121.95,121.65,118.09,24.49；
IR (KBr pellet): vC＝O＝1667.1cm–1。
EXAMPLE 133 preparation of methoxyacetanilide
Taking a 50mL reaction bottle, transferring 3-methoxy acetophenone oxime (0.17g, 1mmol) dissolved in 2mL acetonitrile into the reaction bottle, adding bismuth trifluoromethanesulfonate (0.10g, 0.15mmol) dissolved in 1mL acetonitrile under the condition of stirring, finally adding 2-3mL acetonitrile, and stirring for reaction under the condition of 80 ℃ oil bath. After 3-methoxy acetophenone oxime and bismuth trifluoromethanesulfonate were mixed and stirred, the solution immediately appeared as a white suspension, and the reaction was monitored by TLC (DCM: 100%) until completion, and the reaction proceeded for about 4 hours. Stopping heating, spin-drying the solvent with a rotary evaporator, extracting with water and DCM, combining the organic phases, and extracting with anhydrous Na2SO4And (5) drying. Filtration, concentration, column chromatography (DCM: 100%), spin-drying, pump-drying, weighing of the dried product and calculated yield of 71%.
mp 79-81℃；
1H NMR(400MHz,d6-DMSO,ppm):9.89(s,1H),7.27(s,1H),7.16(t,J＝8.0Hz,1H),7.09(d,J＝8.0Hz,1H),6.59(d,J＝12.0Hz,1H),3.69(s,3H),2.01(s,3H)；
13C NMR(101MHz,d6-DMSO,ppm):168.39,136.83,131.87,130.65,126.28,125.42,125.39,23.72,18.31；
IR (KBr pellet): vC＝O＝1662.87cm–1。
EXAMPLE 14 preparation of o-methylacetanilide
Taking a 50mL reaction bottle, transferring o-methyl acetophenone oxime (0.15g, 1mmol) dissolved in 2mL acetonitrile into the reaction bottle, adding bismuth trifluoromethanesulfonate (0.10g, 0.15mmol) dissolved in 1mL acetonitrile under the condition of stirring, finally adding 2-3mL acetonitrile, and stirring for reaction under the condition of 80 ℃ oil bath. After o-methylacetophenone oxime and bismuth trifluoromethanesulfonate were mixed and stirred, the solution immediately appeared to be a white suspension, and the reaction was monitored by TLC (DCM: 100%) until the reaction was complete and proceeded for about 5 hours. Stopping heating, spin-drying the solvent with a rotary evaporator, extracting with water and DCM, combining the organic phases, and extracting with anhydrous Na2SO4And (5) drying. Filtration, concentration, column chromatography (DCM: 100%), spin-drying, pump-drying, weighing of the dried product and calculated yield of 56%.
mp 107-110℃；
1H NMR(400MHz,d6-DMSO,ppm):9.25(s,1H),7.37(d,J＝8.0Hz,1H),7.17(d,J＝8.0Hz,1H),7.12(t,J＝8.0Hz,1H),7.04(t,J＝8.0Hz,1H),2.17(s,3H),2.03(s,3H)；
13C NMR(101MHz,d6-DMSO,ppm):168.60,136.89,131.95,130.65,126.28,125.42,125.39,23.72,18.31；
IR (KBr pellet): vC＝O＝1489.3cm–1。
EXAMPLE 15 preparation of o-chloroacetanilide
Taking a 50mL reaction bottle, transferring o-chlorobenzeneketoxime (0.17g, 1mmol) dissolved in 2mL acetonitrile into the reaction bottle, adding bismuth trifluoromethanesulfonate (0.10g, 0.15mmol) dissolved in 1mL acetonitrile under the condition of stirring, finally adding 2-3mL acetonitrile, and stirring for reaction under the condition of 80 ℃ oil bath. After the o-chloroacetophenone oxime and bismuth trifluoromethanesulfonate were mixed and stirred, the solution immediately appeared as a colorless solution, which was monitored by TLC (DCM: 100%)The reaction was carried out until the reaction was completed for about 6 hours. Stopping heating, spin-drying the solvent with a rotary evaporator, extracting with water and DCM, combining the organic phases, and extracting with anhydrous Na2SO4And (5) drying. Filtration, concentration, column chromatography (DCM: 100%), spin-drying, pump-drying, weighing of the dried product and calculated yield of 51%.
mp 52.2-57.5℃；
1H NMR(400MHz,d6-DMSO,ppm):9.52(s,1H),7.70(d,J＝8.0Hz,1H),7.48(d,J＝8.0Hz,1H),7.31(t,J＝8.0Hz,1H),7.18(t,J＝6.0Hz,1H),2.09(s,3H)；
13C NMR(101MHz,d6-DMSO,ppm):168.62,135.07,129.41,127.33,126.41,126.31,126.15,23.34；
IR (KBr pellet): vC＝O＝1543.6cm–1。
EXAMPLE 16 preparation of N-phenylcyclohexylcarboxamide
A50 mL reaction flask was taken, cyclohexylphenylketoxime (0.21g, 1mmol) dissolved in 2mL acetonitrile was transferred to the reaction flask, and bismuth trifluoromethanesulfonate (0.10g, 0.15mmol) dissolved in 1mL acetonitrile was added under stirring, and finally 2-3mL acetonitrile was added, and the reaction was stirred in an oil bath at 80 ℃. After the cyclohexylphenylketoxime and bismuth trifluoromethanesulfonate were mixed and stirred, the solution immediately appeared to be a yellow solution, and the reaction was monitored by TLC (DCM: 100%) until completion, and the reaction was carried out for about 5 hours. Stopping heating, spin-drying the solvent with a rotary evaporator, extracting with water and DCM, combining the organic phases, and extracting with anhydrous Na2SO4And (5) drying. Filtration, concentration, column chromatography (DCM: 100%), spin-drying, pump-drying, weighing of the dried product and calculation of yield 76%.
mp 149-150℃；
1H NMR(400MHz,d6-DMSO,ppm):9.76(s,1H),7.58(d,J＝8.0Hz,2H),7.25(t,J＝8.0Hz,2H),6.99(t,J＝6.0Hz,1H),2.30(t,J＝12.0Hz,1H),1.75(t,J＝16.0Hz,4H),1.63(d,J＝12.0Hz,1H),1.43-1.35(m,2H),1.30-1.15(m,3H)；
13C NMR(101MHz,d6-DMSO,ppm):174.70,139.95,129.03,123.26,119.45,45.30,29.59,25.86,25.70；
IR (KBr pellet): vC＝O＝1663.7cm–1。
EXAMPLE 17 preparation of N-thienyl-2-acetamide
A50 mL reaction flask was taken, and (1Z) -1- (2-thiophene) ethanone oxime (0.14g, 1mmol) dissolved in 2mL acetonitrile was transferred to the reaction flask, and bismuth trifluoromethanesulfonate (0.10g, 0.15mmol) dissolved in 1mL acetonitrile was added under stirring, and finally 2-3mL acetonitrile was added, and the reaction was stirred in an oil bath at 80 ℃. After mixing and stirring 1-thiophene-2-methyl-acetophenone oxime and bismuth trifluoromethanesulfonate, the solution immediately appeared as a white suspension, and the reaction was monitored by TLC (DCM: 100%) until the reaction was complete and proceeded for about 10 hours. Stopping heating, spin-drying the solvent with a rotary evaporator, extracting with water and DCM, combining the organic phases, and extracting with anhydrous Na2SO4And (5) drying. Filtration, concentration, column chromatography (DCM: 100%), spin-drying, pump-drying, weighing of the dried product and calculation of the yield to 50%.
mp 155-157℃；
1H NMR(400MHz,d6-DMSO,ppm):11.09(s,1H),6.90(d,J＝4.0Hz,1H),6.82(t,J＝4.0Hz,1H),6.62(dd,J＝4.0Hz,1H),2.05(s,3H)；
13C NMR(101MHz,d6-DMSO,ppm):166.61,140.32,124.27,116.99,110.66,22.95；
IR (KBr pellet): vC＝N＝1644.4cm–1。
Experimental example 1 recovery and recycle of catalyst
The same procedure was followed as in example 1 except that: after the reaction was completed, the reaction solution was poured into a round-bottomed flaskSpin-drying with a rotary evaporator, and recovering acetonitrile serving as a solvent; dichloromethane was added into the round bottom flask, the mixture was extracted by shaking, and the product was dissolved in dichloromethane and the catalyst Bi (OTf)3A white solid precipitated. Filtering, drying the filter residue, and recovering to obtain Bi (OTf)3。
The catalyst Bi (OTf) recovered above3And (4) repeating the steps, and circulating the steps until the catalyst has no catalytic effect. The results of the experiment are shown in table 1 below:
TABLE 1
| Number of cycles | Yield of dibenzoyl amide |
| 1 | >99％ |
| 2 | 86％ |
| 3 | 47％ |
| 4 | Trace amount of product |
As can be seen from the data in the table, the yield of the catalyst bismuth trifluoromethanesulfonate is obviously reduced after the catalyst bismuth trifluoromethanesulfonate is utilized for the third time. The main reasons are that the catalytic effect of the catalyst is reduced, the conversion rate is low, the reaction is incomplete, and the product contains a large amount of raw materials. By the fourth time, there was little reaction and very little product could be detected by HPLC. Therefore, the optimum number of times of use of the catalyst is two, and the yield is rapidly decreased at the third use.
Experimental example 2 Effect of catalyst type on Beckmann rearrangement
The synthesis of dibenzoyl amide was carried out according to the procedure of example 1, using the catalysts shown in the following table 2, respectively, and the experimental results are shown in the following table 2:
TABLE 2 Effect of the catalyst on the reaction
As can be seen from the results in the table, except ZnCl2And MgCl2Besides, other Lewis catalysts have certain catalytic effect on the reaction. Wherein AlCl3、BF3And Bi (OTf)3The catalytic effect is best, and almost complete conversion is achieved. But using AlCl3When the catalyst is used, one is strict on the solvent, anhydrous treatment is required, and the treatment after the reaction is troublesome because AlCl3When water is used, the water is hydrolyzed to become white and turbid, so that the water is inconvenient to use. By BF3Although the post-treatment of the catalyst is simple, the catalyst can be removed only by rotary evaporation, but BF is caused3Is very easy to absorb water, needs anhydrous and oxygen-free operation, and is inconvenient to use because the solvent needs water removal treatment. And Bi (OTf)3No toxicity, water solubility, direct extraction after post treatment, simple operation and easy implementation.
Claims (10)
1. The application of bismuth trifluoromethanesulfonate as a catalyst for Beckmann rearrangement reaction is characterized in that under the catalytic action of bismuth trifluoromethanesulfonate, ketoxime is subjected to Beckmann rearrangement reaction and converted into amide, wherein in the Beckmann rearrangement reaction, a solvent is acetonitrile, toluene or benzene; the ketoxime is represented by the following general formula:
wherein R is1And R2Each is independentThe standing place is as follows: substituted or unsubstituted alkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted cycloalkyl.
2. Use according to claim 1, wherein the bismuth triflate is used in an amount of 10 to 20% in moles of the ketoxime in the Beckmann rearrangement reaction relative to the moles of the ketoxime.
3. The use according to claim 1, wherein the alkyl group is a C1-C6 alkyl group; the aryl is phenyl, thienyl or furyl; the cycloalkyl is cyclopentyl or cyclohexyl;
the substituted is alkyl, aryl or cycloalkyl substituted by a substituent selected from methyl, methoxy, fluorine, chlorine, bromine and hydroxyl.
4. Use according to claim 3, characterized in that the ketoxime is chosen from among benzophenone oxime, 4 ' -dimethyl-benzophenone oxime, 4 ' -dimethoxy-benzophenone oxime, 4 ' -difluoro-benzophenone oxime, acetophenone oxime, p-fluoro-acetophenone oxime, p-chlorophenyl-acetophenone oxime, p-hydroxy-acetophenone oxime, p-methyl-acetophenone oxime, p-methoxy-acetophenone oxime, m-hydroxy-acetophenone oxime, 3-bromo-acetophenone oxime, 3-methoxy-acetophenone oxime, o-methyl-acetophenone oxime, o-chlorophenyl-acetophenone oxime, cyclohexyl-phenyl-ketone oxime and 2-thienyl-ethyl-ketone oxime.
5. Use according to claim 1, wherein the solvent is acetonitrile in the Beckmann rearrangement reaction.
6. The use according to claim 1, wherein the reaction temperature is 50 ℃ to 100 ℃ and the reaction time is 0.5 to 10 hours in the Beckmann rearrangement reaction.
7. A method for preparing amide comprises the steps of carrying out Beckmann rearrangement reaction on ketoxime by taking bismuth trifluoromethanesulfonate as a catalyst to convert the ketoxime into the amide, wherein in the Beckmann rearrangement reaction, a solvent is acetonitrile, toluene or benzene; the ketoxime is represented by the following general formula:
wherein R is1And R2Each independently is: substituted or unsubstituted alkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted cycloalkyl.
8. The method according to claim 7, wherein the alkyl group is a C1-C6 alkyl group; the aryl is phenyl, thienyl or furyl; the cycloalkyl is cyclopentyl or cyclohexyl;
the substituent means that the alkyl, the aryl or the cycloalkyl is substituted by a substituent selected from methyl, methoxy, fluorine, chlorine, bromine and hydroxyl;
in the Beckmann rearrangement reaction, the dosage of the bismuth trifluoromethanesulfonate is 10-20% of the molar number of the ketoxime.
9. The process for producing amides according to claim 8, wherein said ketoxime is selected from the group consisting of benzophenone oxime, 4 ' -dimethylbenzophenone oxime, 4 ' -dimethoxybenzophenone oxime, 4 ' -difluorobenzophenone oxime, acetophenone oxime, p-fluoroacetophenone oxime, p-chloroacetophenone oxime, p-hydroxyacetophenone oxime, p-methylacetophenone oxime, p-methoxyacetophenone oxime, m-hydroxyacetophenone oxime, 3-bromoacetophenone oxime, 3-methoxyacetophenone oxime, o-methylacetophenone oxime, o-chloroacetophenone oxime, cyclohexylbenzophenone oxime and 2-thienylacetophenone oxime.
10. The process according to claim 7, wherein the solvent is acetonitrile; the reaction temperature is 50-100 ℃; the reaction time is 0.5 to 10 hours.
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| [Yb(OTf)3] catalysed facile conversion of ketoximes to amides and lactams;J.S. Yadav et al.;《Journal of Chemical Research(s)》;20021231;第236-238页 * |
| Microwave Induced Bismuth Trichloride Catalysed Beckmann Rearrangement of Oximes;Ashim J. Thakur et al.;《Synthetic Communications》;20071204;第30卷(第12期);第2105-2111页 * |
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