CN115108976B - 一种一步氧化酰胺化制备吡啶甲酰胺的方法 - Google Patents
一种一步氧化酰胺化制备吡啶甲酰胺的方法 Download PDFInfo
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- CN115108976B CN115108976B CN202110290256.0A CN202110290256A CN115108976B CN 115108976 B CN115108976 B CN 115108976B CN 202110290256 A CN202110290256 A CN 202110290256A CN 115108976 B CN115108976 B CN 115108976B
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- Prior art keywords
- pyridine
- catalyst
- methanol
- ammonium
- pyridine carboxamide
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- IBBMAWULFFBRKK-UHFFFAOYSA-N picolinamide Chemical compound NC(=O)C1=CC=CC=N1 IBBMAWULFFBRKK-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000009435 amidation Effects 0.000 title claims abstract description 15
- 238000007112 amidation reaction Methods 0.000 title claims abstract description 15
- 230000003647 oxidation Effects 0.000 title claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- SHNUBALDGXWUJI-UHFFFAOYSA-N pyridin-2-ylmethanol Chemical compound OCC1=CC=CC=N1 SHNUBALDGXWUJI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 15
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 35
- 238000002360 preparation method Methods 0.000 claims description 24
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 14
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 229920000877 Melamine resin Polymers 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- 239000002904 solvent Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 150000003682 vanadium compounds Chemical class 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- 229920000767 polyaniline Polymers 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 2
- DGZXMSLLXBWIFG-UHFFFAOYSA-N formaldehyde;pyridine Chemical compound O=C.C1=CC=NC=C1 DGZXMSLLXBWIFG-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 33
- 239000000843 powder Substances 0.000 description 32
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 16
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 238000004817 gas chromatography Methods 0.000 description 9
- 238000000227 grinding Methods 0.000 description 9
- 239000004570 mortar (masonry) Substances 0.000 description 9
- 229910052573 porcelain Inorganic materials 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000007790 solid phase Substances 0.000 description 9
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 5
- 229940041260 vanadyl sulfate Drugs 0.000 description 5
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 5
- MVQVNTPHUGQQHK-UHFFFAOYSA-N 3-pyridinemethanol Chemical compound OCC1=CC=CN=C1 MVQVNTPHUGQQHK-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229960003966 nicotinamide Drugs 0.000 description 4
- 235000005152 nicotinamide Nutrition 0.000 description 4
- 239000011570 nicotinamide Substances 0.000 description 4
- PTMBWNZJOQBTBK-UHFFFAOYSA-N pyridin-4-ylmethanol Chemical compound OCC1=CC=NC=C1 PTMBWNZJOQBTBK-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- YVUBWJOBCFNMES-UHFFFAOYSA-N formamide;pyridine Chemical compound NC=O.C1=CC=NC=C1 YVUBWJOBCFNMES-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZRJJXXDQIQFZBW-UHFFFAOYSA-N (2-aminopyridin-4-yl)methanol Chemical compound NC1=CC(CO)=CC=N1 ZRJJXXDQIQFZBW-UHFFFAOYSA-N 0.000 description 2
- UEAIOHHGRGSGGJ-UHFFFAOYSA-N (4-chloropyridin-2-yl)methanol Chemical compound OCC1=CC(Cl)=CC=N1 UEAIOHHGRGSGGJ-UHFFFAOYSA-N 0.000 description 2
- FMZXNVLFJHCSAF-DNVCBOLYSA-N (6R,7R)-3-[(4-carbamoyl-1-pyridin-1-iumyl)methyl]-8-oxo-7-[(1-oxo-2-thiophen-2-ylethyl)amino]-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate Chemical compound C1=CC(C(=O)N)=CC=[N+]1CC1=C(C([O-])=O)N2C(=O)[C@@H](NC(=O)CC=3SC=CC=3)[C@H]2SC1 FMZXNVLFJHCSAF-DNVCBOLYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-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
- SSLIBLGVKYPVPA-UHFFFAOYSA-N N#[C-].C1=CC=NC=C1 Chemical class N#[C-].C1=CC=NC=C1 SSLIBLGVKYPVPA-UHFFFAOYSA-N 0.000 description 2
- JLYYQZROGJLCCS-UHFFFAOYSA-N [6-(bromomethyl)pyridin-2-yl]methanol Chemical compound OCC1=CC=CC(CBr)=N1 JLYYQZROGJLCCS-UHFFFAOYSA-N 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000002862 amidating effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 229950005258 cefalonium Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- AGSDASDGMNDAIE-UHFFFAOYSA-N 2-aminopyridine-4-carboxamide Chemical compound NC(=O)C1=CC=NC(N)=C1 AGSDASDGMNDAIE-UHFFFAOYSA-N 0.000 description 1
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- XIHHOUUTBZSYJH-UHFFFAOYSA-N 4-chloropyridine-2-carboxamide Chemical compound NC(=O)C1=CC(Cl)=CC=N1 XIHHOUUTBZSYJH-UHFFFAOYSA-N 0.000 description 1
- 208000005232 Glossitis Diseases 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- BAWFJGJZGIEFAR-NNYOXOHSSA-N NAD zwitterion Chemical compound NC(=O)C1=CC=C[N+]([C@H]2[C@@H]([C@H](O)[C@@H](COP([O-])(=O)OP(O)(=O)OC[C@@H]3[C@H]([C@@H](O)[C@@H](O3)N3C4=NC=NC(N)=C4N=C3)O)O2)O)=C1 BAWFJGJZGIEFAR-NNYOXOHSSA-N 0.000 description 1
- XJLXINKUBYWONI-NNYOXOHSSA-N NADP zwitterion Chemical compound NC(=O)C1=CC=C[N+]([C@H]2[C@@H]([C@H](O)[C@@H](COP([O-])(=O)OP(O)(=O)OC[C@@H]3[C@H]([C@@H](OP(O)(O)=O)[C@@H](O3)N3C4=NC=NC(N)=C4N=C3)O)O2)O)=C1 XJLXINKUBYWONI-NNYOXOHSSA-N 0.000 description 1
- 206010029400 Nicotinic acid deficiency Diseases 0.000 description 1
- 208000002141 Pellagra Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- VFQXVTODMYMSMJ-UHFFFAOYSA-N isonicotinamide Chemical compound NC(=O)C1=CC=NC=C1 VFQXVTODMYMSMJ-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WKHYEFMJDLHERO-UHFFFAOYSA-N methanol;2-methylpyridine Chemical compound OC.CC1=CC=CC=N1 WKHYEFMJDLHERO-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229950006238 nadide Drugs 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 150000003140 primary amides Chemical class 0.000 description 1
- UZFKIHMFDWGBKC-UHFFFAOYSA-N pyridine-4-carboxamide Chemical compound NC(=O)C1=CC=NC=C1.NC(=O)C1=CC=NC=C1 UZFKIHMFDWGBKC-UHFFFAOYSA-N 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 208000003265 stomatitis Diseases 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明提供了一种一步氧化酰胺化制备吡啶甲酰胺的方法，属于精细化学品的技术领域。该方法是一种以吡啶甲醇或吡啶甲醛为原料，以分子氧为氧化剂，采用V‑N‑C材料作为多相催化剂，在含氮化合物的存在下，通过一步液相催化氧化酰胺化制备吡啶甲酰胺的新方法。该方法反应温度为60‑160℃，氧气分压为0.1‑2MPa，不以吡啶甲腈为中间体，具有反应条件温和、安全环保，催化剂和产品易于从反应体系分离等优点。
Description
技术领域
本发明属于精细化学品的技术领域，具体涉及到一种以吡啶甲醇或吡啶甲醛为原料，以分子氧为氧化剂，采用V-N-C多相催化剂，通过一步液相催化氧化酰胺化制备吡啶甲酰胺的新方法。
背景技术
吡啶甲酰胺是一类重要的含氮杂环化合物，在医药、日化等领域具有重要应用。例如3-吡啶甲酰胺(烟酰胺)，是辅酶I和辅酶Ⅱ等的组成部分之一，在医学上主要用于防治糙皮病、口炎、舌炎等。此外，3-吡啶甲酰胺还大量用作食品、饲料添加剂以及日化用品中的美白成分。4-吡啶甲酰胺(异烟酰胺)可用作医药中间体，主要用于合成头孢洛宁(Cefalonium)等。
吡啶甲酰胺等酰胺类化合物最常用的合成方法是由羧酸及其衍生物(包括酰氯，酸酐和酯等)与氨/胺的反应。羧酸与胺的直接缩合反应是一个可逆反应，通常需要通过加入过量的反应物或者在反应过程中除水的方法来提高反应收率。采用反应活性高的酰氯容易得到酰胺，但这种方法需要预先得到酰氯等化合物，且反应需要消耗碱性物质作为束酸剂，例如工业上使用苯甲酰氯与氨反应制备苯甲酰胺。在以醇或醛为底物合成酰胺的方法中，Yamaguchi K等使用锰氧化物八面体分子筛(OMS-2)作为催化剂，能够将伯醇或醛氧化转化为相应的伯酰胺(Catal.Sci.Technol.,2013,3,318-327)，但这一催化体系容易生成大量腈类副产物，需要严格控制反应条件。中国发明专利(CN 104072409A)则通过用吡啶氰类化合物为原料，在沸石ETS-10分子筛的催化作用下，通过水解反应得到吡啶酰胺类化合物，这种方法主要受制于原料吡啶氰的市场供应。开发廉价高效、环境友好的吡啶甲酰胺的制备新方法仍然具有重要意义和应用背景。
本发明以分子氧为氧源，以V-N-C材料为多相催化剂，将吡啶甲醇/吡啶甲醛一步氧化酰胺化为吡啶甲酰胺，反应条件温和，副产物吡啶甲腈生成少。
发明内容
本发明的目的在于提供了一种吡啶甲醇/吡啶甲醛氧化酰胺化制备吡啶甲酰胺的新方法。该方法是一种以吡啶甲醇/吡啶甲醛为原料，以分子氧为氧化剂，采用V-N-C多相催化剂，通过一步液相催化氧化酰胺化制备吡啶甲酰胺的新方法。
为了达到上述目的，本发明采用的技术方案为：
一种一步氧化酰胺化制备吡啶甲酰胺的方法，该方法是以V-N-C材料为多相催化剂，以分子氧为氧源，在含氮化合物存在下，在溶剂中将吡啶甲醇/吡啶甲醛一步氧化酰胺化为吡啶甲酰胺，包括以下步骤：
将吡啶甲醇/吡啶甲醛、V-N-C催化剂、含氮化合物、溶剂投入反应釜中，再通入分子氧作为氧源，密闭反应釜后，搅拌加热升温至60-160℃，反应时间不大于12h，然后冷却到室温，释放压力，过滤掉催化剂后，分离得到吡啶甲酰胺。取样用GC分析产物，并用吡啶甲酰胺及吡啶甲醇/吡啶甲醛标准品与产物主要组分的色谱保留时间进行比对，确定主要产物。
进一步的，所述的吡啶甲醇/吡啶甲醛为Ⅰ、Ⅱ结构式中一种或二种混合物，对应吡啶甲酰胺结构式为Ⅲ。
所述的吡啶甲醇/吡啶甲醛为Ⅰ、Ⅱ结构式中羟甲基和醛基在吡啶环上的α位、β位或γ位。含有的取代基R为H、烷基、苯基、卤素、硝基、氰基、氨基、甲氧基、乙氧基、乙酰氨基或乙酰氧基中一种或者两种以上组合，所述取代基R的个数为一个或一个以上，R取代基的位置为邻位、间位或对位中一种或多种；R为H即表示吡啶环上只有羟甲基或醛基，对应吡啶甲酰胺结构式为Ⅲ。。
进一步的，所述的溶剂为水、甲苯、对二甲苯、邻二甲苯、间二甲苯、乙苯、N,N-二甲基甲酰胺、二甲基亚砜、环己烷、正己烷、二氯甲烷、乙酸乙酯、乙酸丁酯、甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丙醇、乙腈、苯乙腈中一种或者多种，溶剂用量为原料吡啶甲醇/吡啶甲醛质量的0.2-20倍。
进一步的，所述的催化剂为V-N-C材料，其用量为原料吡啶甲醇/吡啶甲醛投料量的1-40wt％；反应中的分子氧来自空气、氧气或者含有氧气的气体，氧气分压为0.1-2MPa。
进一步的，所述V-N-C材料催化剂是以一定比例的无机钒化合物与有机胺混合后经热处理制备，制备的方法如下：将一定量无机钒化合物与有机胺混合，将此混合物在300-1000℃的条件下惰性气氛中煅烧0.5-20h后冷却，得到V-N-C材料催化剂。所述的无机钒化合物为硫酸氧钒、偏钒酸铵、偏钒酸钠、二氧化钒、五氧化二钒中一种或多种，所述的有机胺为聚苯胺、二乙烯二胺、三聚氰胺中一种或多种，有机胺中的胺基与无机钒化合物中的钒摩尔比为1:1-1:6。
进一步的，所述催化剂制备过程中的惰性气氛为氮气、氩气中一种或者一种以上混合物。
进一步的，所述的含氮化合物为尿素、甲酰胺、乙酰胺、氨水、碳酸铵、碳酸氢铵、氨基甲酸铵、甲酸铵、乙酸铵、磷酸铵、磷酸氢二铵、硫酸氢铵、硫酸铵、硝酸铵、氯化铵中一种或者多种，含氮化合物用量为原料吡啶甲醇/吡啶甲醛摩尔量的0.2-10倍。
本发明的有益效果为：
本发明提供了一种吡啶甲醇/吡啶甲醛氧化酰胺化制备吡啶甲酰胺的新方法，该方法是以分子氧为氧化剂，反应条件温和、安全环保；原料吡啶甲醇/吡啶甲醛一步直接转化为吡啶甲酰胺，副产物吡啶甲腈生成少，具有广阔的应用前景。
附图说明
图1为实施例1为2-吡啶甲醇催化氧化酰胺化制备2-吡啶甲酰胺的GC谱图。
图2为实施例2为2-吡啶甲醇催化氧化酰胺化制备2-吡啶甲酰胺的GC谱图。
具体实施方式
将吡啶甲醇/吡啶甲醛、V-N-C催化剂、含氮化合物、溶剂投入反应釜中，再通入分子氧作为氧源，密闭反应釜后，搅拌加热升温反应，然后冷却到室温，释放压力，过滤掉催化剂后，分离得到吡啶甲酰胺。取样用GC分析产物。
下面通过实施例详述本发明的技术方案，但本发明的保护范围不限于此。
实施例1：A催化剂的制备和反应结果
V-N-C材料制备过程采用摩尔比为三聚氰胺和偏钒酸铵(1:3)制备：分别取2.0g三聚氰胺和5.6g偏钒酸铵粉末倒入研钵中进行固相机械研磨，所得粉末用瓷舟装载煅烧，在氮气氛围、700℃下利用管式炉中进行煅烧，升温速率10℃/min，恒温1.5h后在氮气气氛下降至室温，得到黑色V-N-C固体粉末，记为催化剂A。
将5mmol2-吡啶甲醇、5mmol尿素、10wt％催化剂A、2mL乙腈加入到50mL反应釜中，充入0.5MPa氧气，搅拌下升温至100℃，运行4h。然后冷却到室温，小心减压到常压。取样用气相色谱进行产物定量分析，2-吡啶甲醇的转化率99％，2-吡啶甲酰胺的选择性91％(图1)。反应结果见表1。
实施例2：除加入反应釜的催化剂A为1％，其他按照实施例1中的制备方法。
除催化剂用量不同外，投料量和反应条件与实施例1中的反应部分相同，取样用气相色谱进行产物定量分析，2-吡啶甲醇的转化率94％，2-吡啶甲酰胺的选择性69％(图2)。
实施例3：B催化剂的制备和反应结果
V-N-C材料制备过程采用摩尔比为三聚氰胺和二氧化钒(1:2)制备：分别取1.0g三聚氰胺和1.3g二氧化钒粉末倒入研钵中进行固相机械研磨，所得粉末用瓷舟装载煅烧，在氮气氛围、500℃下利用管式炉中进行煅烧，升温速率5℃/min，恒温3h后在氮气气氛下降至室温，得到黑色V-N-C固体粉末，记为催化剂B。
将5mmol4-吡啶甲醇、5mmol甲酰胺、10wt％催化剂B、2mL甲苯加入到50mL反应釜中，充入0.5MPa空气，搅拌下升温至120℃，运行6h。然后冷却到室温，小心减压到常压。取样用气相色谱进行产物定量分析，4-吡啶甲醇的转化率97％，4-吡啶甲酰胺的选择性85％。反应结果见表1。
实施例4：C催化剂的制备和反应结果
V-N-C材料制备过程采用摩尔比为二乙烯二胺和硫酸氧钒(1:4)制备：分别取2.0g二乙烯二胺和15.1g硫酸氧钒粉末倒入研钵中进行固相机械研磨，所得粉末用瓷舟装载煅烧，在氩气氛围、900℃下利用管式炉中进行煅烧，升温速率5℃/min，恒温6h后在氩气气氛下降至室温，得到黑色V-N-C固体粉末，记为催化剂C。
将5mmol3-吡啶甲醇、10mmol氨水(28％)、20wt％催化剂C、4mL对二甲苯加入到50mL反应釜中，充入1.0MPa含有氧气的气体，搅拌下升温至160℃，运行8h。然后冷却到室温，小心减压到常压。取样用气相色谱进行产物定量分析，3-吡啶甲醇的转化率96％，3-吡啶甲酰胺的选择性92％。反应结果见表1。
实施例5：D催化剂的制备和反应结果
V-N-C材料制备过程采用摩尔比为二乙烯二胺和五氧化二钒(1:1)制备：分别取2.0g二乙烯二胺和4.2g五氧化二钒粉末倒入研钵中进行固相机械研磨，所得粉末用瓷舟装载煅烧，在氮气氛围、1000℃下利用管式炉中进行煅烧，升温速率10℃/min，恒温2h后在氮气气氛下降至室温，得到黑色V-N-C固体粉末，记为催化剂D。
将5mmol4-氯-2-吡啶甲醇、20mmol碳酸氢铵、10wt％催化剂D、6mLN,N-二甲基甲酰胺加入到50mL反应釜中，充入2.0MPa含有氧气的气体，搅拌下升温至80℃，运行4h。然后冷却到室温，小心减压到常压。取样用气相色谱进行产物定量分析，4-氯-2-吡啶甲醇的转化率92％，4-氯-2-吡啶甲酰胺的选择性84％。反应结果见表1。
实施例6：E催化剂的制备和反应结果
V-N-C材料制备过程采用摩尔比为二乙烯二胺和偏钒酸钠(1:6)制备：分别取0.5g二乙烯二胺和4.2g偏钒酸钠粉末倒入研钵中进行固相机械研磨，所得粉末用瓷舟装载煅烧，在氮气氛围、300℃下利用管式炉中进行煅烧，升温速率10℃/min，恒温10h后在氮气气氛下降至室温，得到黑色V-N-C固体粉末，记为催化剂E。
将5mmol2-氨基-4-吡啶甲醇、50mmol乙酸铵、30wt％催化剂E、10mL二甲基亚砜加入到50mL反应釜中，充入1.0MPa氧气，搅拌下升温至60℃，运行6h。然后冷却到室温，小心减压到常压。取样用气相色谱进行产物定量分析，2-氨基-4-吡啶甲醇的转化率95％，2-氨基-4-吡啶甲酰胺的选择性90％。反应结果见表1。
实施例7：F催化剂的制备和反应结果
V-N-C材料制备过程采用摩尔比为三聚氰胺和五氧化二钒(1:5)制备：分别取1.0g三聚氰胺和7.2g五氧化二钒粉末倒入研钵中进行固相机械研磨，所得粉末用瓷舟装载煅烧，在氮气氛围、600℃下利用管式炉中进行煅烧，升温速率10℃/min，恒温3h后在氩气气氛下降至室温，得到黑色V-N-C固体粉末，记为催化剂F。
将5mmol2-吡啶甲醇和5mmol吡啶-2-甲醛、10mmol磷酸铵、10wt％催化剂F、20mL二氯甲烷加入到50mL反应釜中，充入2.0MPa氧气，搅拌下升温至80℃，运行8h。然后冷却到室温，小心减压到常压。取样用气相色谱进行产物定量分析，2-吡啶甲醇的转化率90％，2-吡啶甲酰胺的选择性84％。反应结果见表1。
实施例8：G催化剂的制备和反应结果
V-N-C材料制备过程采用摩尔比为三聚氰胺、二乙烯二胺和硫酸氧钒(1:1:2)制备：分别取1.0g三聚氰胺、0.7g二乙烯二胺和2.6g硫酸氧钒粉末倒入研钵中进行固相机械研磨，所得粉末用瓷舟装载煅烧，在氩气氛围、800℃下利用管式炉中进行煅烧，升温速率5℃/min，恒温5h后在氩气气氛下降至室温，得到黑色V-N-C固体粉末，记为催化剂G。
将5mmol6-溴甲基-2-吡啶甲醇、10mmol硫酸氢铵、40wt％催化剂F、2mL乙酸乙酯和2mL乙酸丁酯加入到50mL反应釜中，充入0.5MPa氧气，搅拌下升温至100℃，运行8h。然后冷却到室温，小心减压到常压。取样用气相色谱进行产物定量分析，6-溴甲基-2-吡啶甲醇的转化率94％，6-溴甲基-2-吡啶甲酰胺的选择性87％。反应结果见表1。
实施例9：H催化剂的制备和反应结果
V-N-C材料制备过程采用摩尔比为聚苯胺和二氧化钒(1:2)制备：分别取1.0g聚苯胺和1.8g二氧化钒粉末倒入研钵中进行固相机械研磨，所得粉末用瓷舟装载煅烧，在氩气氛围、600℃下利用管式炉中进行煅烧，升温速率10℃/min，恒温16h后在氮气气氛下降至室温，得到黑色V-N-C固体粉末，记为催化剂H。
将5mmol2,6-二溴-4-甲醇吡啶、10mmol氨基甲酸铵和10mmol甲酸铵、10wt％催化剂H、10mL甲醇加入到50mL反应釜中，充入1.0MPa氧气，搅拌下升温至120℃，运行6h。然后冷却到室温，小心减压到常压。取样用气相色谱进行产物定量分析，2,6-二溴-4-甲醇吡啶的转化率96％，2,6-二溴-4-甲酰胺吡啶的选择性88％。反应结果见表1。
实施例10：I催化剂的制备和反应结果
V-N-C材料制备过程采用摩尔比为聚苯胺和偏钒酸铵(1:4)制备：分别取1.0g聚苯胺和2.6g偏钒酸铵粉末倒入研钵中进行固相机械研磨，所得粉末用瓷舟装载煅烧，在氮气氛围、400℃下利用管式炉中进行煅烧，升温速率10℃/min，恒温4h后在氮气气氛下降至室温，得到黑色V-N-C固体粉末，记为催化剂I。
将5mmol2吡啶甲醇、10mmol氯化铵、10wt％催化剂I、10mL正丙醇加入到50mL反应釜中，充入2.0MPa氧气，搅拌下升温至80℃，运行4h。然后冷却到室温，小心减压到常压。取样用气相色谱进行产物定量分析，2-吡啶甲醇的转化率97％，2-吡啶甲酰胺的选择性87％。反应结果见表1。
表1.不同催化剂组成和添加含氮化合物及其各个反应结果
以上所述实施例仅表达本发明的实施方式，但并不能因此而理解为对本发明专利范围的限制，应当指出，对于本领域的技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些均属于本发明的保护范围。
Claims (6)
1.一种一步氧化酰胺化制备吡啶甲酰胺的方法，其特征在于，该方法是以V-N-C材料为多相催化剂，以分子氧为氧源，在含氮化合物存在下，在溶剂中将吡啶甲醇一步氧化酰胺化为吡啶甲酰胺，具体步骤如下：
将吡啶甲醇、V-N-C催化剂、含氮化合物、溶剂投入反应釜中，再通入分子氧作为氧源，密闭反应釜后，搅拌加热升温至60-160℃，反应时间不大于12h，然后冷却到室温，释放压力，过滤掉催化剂后，分离得到吡啶甲酰胺；
所述的催化剂用量为原料吡啶甲醇投料量的1-40wt％；反应中的分子氧来自空气、氧气，氧气分压为0.1-2MPa；
所述的吡啶甲醇为Ⅰ结构式，对应吡啶甲酰胺结构式为Ⅲ；
其中，含有的取代基R为H、烷基、苯基、卤素、硝基、氰基、氨基、甲氧基、乙氧基、乙酰氨基或乙酰氧基中一种或者两种以上组合，当R为H时，表示吡啶环上只有羟甲基；所述取代基R的个数为一个或一个以上，R取代基的位置为邻位、间位或对位中一种或多种；
所述的含氮化合物为尿素、甲酰胺、碳酸氢铵、甲酸铵、乙酸铵、磷酸铵、硫酸氢铵、氯化铵中的一种；
所述V-N-C材料催化剂是以一定比例的无机钒化合物与有机胺混合后经热处理制备，制备的方法如下：将无机钒化合物与有机胺混合，将此混合物在300-1000℃的条件下惰性气氛中煅烧0.5-20h后冷却，得到V-N-C材料催化剂；所述的有机胺中的胺基与无机钒化合物中的钒摩尔比为1:1-1:6；所述的无机钒化合物为偏钒酸铵、偏钒酸钠、二氧化钒、五氧化二钒中一种，所述的有机胺为聚苯胺、二乙烯二胺、三聚氰胺中一种。
2.根据权利要求1所述的一种一步氧化酰胺化制备吡啶甲酰胺的方法，其特征在于，所述的吡啶甲醇为Ⅰ结构式。
3.根据权利要求1或2所述的一种一步氧化酰胺化制备吡啶甲酰胺的方法，其特征在于，所述的溶剂为水、甲苯、对二甲苯、邻二甲苯、间二甲苯、乙苯、N,N-二甲基甲酰胺、二甲基亚砜、环己烷、正己烷、二氯甲烷、乙酸乙酯、乙酸丁酯、甲醇、乙醇、正丙醇、异丙醇、正丁醇、乙腈、苯乙腈中一种或者多种。
4.根据权利要求3所述的一种一步氧化酰胺化制备吡啶甲酰胺的方法，其特征在于，所述的溶剂用量为原料吡啶甲醇质量的0.2-20倍。
5.根据权利要求1所述的一种一步氧化酰胺化制备吡啶甲酰胺的方法，其特征在于，所述的含氮化合物用量为原料吡啶甲醇摩尔量的0.2-10倍。
6.根据权利要求1所述的一种一步氧化酰胺化制备吡啶甲酰胺的方法，其特征在于，所述催化剂制备过程中的惰性气氛为氮气、氩气中一种或者一种以上混合物。
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