CN111574477A - 一种酰胺类化合物的合成方法 - Google Patents
一种酰胺类化合物的合成方法 Download PDFInfo
- Publication number
- CN111574477A CN111574477A CN202010139172.2A CN202010139172A CN111574477A CN 111574477 A CN111574477 A CN 111574477A CN 202010139172 A CN202010139172 A CN 202010139172A CN 111574477 A CN111574477 A CN 111574477A
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- China
- Prior art keywords
- amide
- synthesizing
- benzyl alcohol
- water
- catalyst
- Prior art date
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- Granted
Links
- -1 amide compound Chemical class 0.000 title claims abstract description 37
- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000011941 photocatalyst Substances 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000013032 photocatalytic reaction Methods 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000007787 solid Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 229920000877 Melamine resin Polymers 0.000 claims description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 14
- 230000002194 synthesizing effect Effects 0.000 claims description 14
- 150000001408 amides Chemical class 0.000 claims description 13
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000012312 sodium hydride Substances 0.000 claims description 9
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 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
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 125000004214 1-pyrrolidinyl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 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 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 5
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 1
- 229910052732 germanium Inorganic materials 0.000 claims 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 description 18
- 239000007788 liquid Substances 0.000 description 14
- 238000005286 illumination Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 10
- BAULSHLTGVOYKM-UHFFFAOYSA-N n-butylbenzamide Chemical compound CCCCNC(=O)C1=CC=CC=C1 BAULSHLTGVOYKM-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 238000001819 mass spectrum Methods 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- RYGJQVQEGCQNHM-UHFFFAOYSA-N n,n-dibutylbenzamide Chemical compound CCCCN(CCCC)C(=O)C1=CC=CC=C1 RYGJQVQEGCQNHM-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- YMDCAYHEWFKCFR-UHFFFAOYSA-N 1-hydroxy-1-oxidopiperidin-1-ium Chemical compound O[N+]1([O-])CCCCC1 YMDCAYHEWFKCFR-UHFFFAOYSA-N 0.000 description 1
- KMTDMTZBNYGUNX-UHFFFAOYSA-N 4-methylbenzyl alcohol Chemical compound CC1=CC=C(CO)C=C1 KMTDMTZBNYGUNX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- YTRCVQWXYYPLAA-UHFFFAOYSA-N [GeH3+]=O Chemical compound [GeH3+]=O YTRCVQWXYYPLAA-UHFFFAOYSA-N 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- WGQKYBSKWIADBV-UHFFFAOYSA-N aminomethyl benzene Natural products NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
- C07D295/182—Radicals derived from carboxylic acids
- C07D295/192—Radicals derived from carboxylic acids from aromatic carboxylic 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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Abstract
本发明公开了一种酰胺类化合物的合成方法,将具有式(I)结构的苄醇与具有式(II)结构的胺类化合物以有机溶剂作为媒介,在光催化剂负载金属P‑C3N4存在的条件下经光催化反应制得具有式(III)结构的酰胺类化合物;该合成方法无需使用热源供热,避免了高温反应,操作简单,反应时间短,后处理简单,易于实现工业化生产。
Description
技术领域
本发明属于光催化合成酰胺技术领域,涉及一种酰胺类化合物的合成方法,特别涉及一种采用负载金属P-C3N4催化剂光催化苄醇与胺直接脱氢合成酰胺类化合物的方法。
背景技术
酰胺键作为构建蛋白质的关键官能团,它是构成生物肽和蛋白质的结构单元。酰胺键的合成方法主要有:缩合法、酰卤法、混合酸酐法以及酰基迭氮法。专利CN 106279013A和CN101842154 A公开了一种采用金属氧化物作催化剂,将羧酸和胺发生催化反应,合成酰胺的方法,该方法通过加热共沸,除去反应生成的水。CN104058983 A公开了一种医药中间体酰胺化合物的合成方法,该方法以PPh3/CBr4/助剂为复合催化剂,在甲苯溶剂中,实现不活泼羧酸与胺类的酰化反应。传统的酰胺合成采用羧酸为原料,再与胺通过亲核取代反应进行酰化作用。从原子经济性来说,此类方法在使用过程中存在废弃物多、后处理过程复杂、原子经济性差、反应温度高,不利于大规模生产。现有方法需在大量的有机溶剂体系中发生反应,都需要后续的溶剂回收处理,反应时间也相对较长,不利于工业化生产。
由醇和胺直接脱氢偶联一步生成酰胺,反应副产物仅为氢气,原子经剂性高,CN107335439A公开了一种氮掺杂碳硅基双金属催化剂,催化醇胺脱氢合成酰胺的方法。专利CN201210188466.X公开了石墨烯负载二氧化锰催化醇与氨水制备酰胺的方法。已有热催化醇胺偶联存在:1)催化剂与产物的分离是难,增加了工业生产成本;2)传统热催化大多采用过量的过氧化物作氧化剂,过氧化物对热不稳定的物质,容易自分解放出大量热,容易引起危害事故,不利于工业生产;3)催化反应大多需要高温(高于110℃),高温下反应选择性不高,导致产物复杂。由于光催化选择性氧化技术具有反应条件温和(通常室温下进行)、反应过程绿色、目标产物选择性高的优点而备受研究者们的关注。采用光催化苯甲醇制备酰胺还未见报道,随着我国环境保护的日益重视,绿色、高效、经济地由醇和胺光催化合成酰胺的制备方法值得进一步去发展。
发明内容
针对现有技术中存在的上述技术问题,本发明提供了一种酰胺类化合物的合成方法,避免了高温反应、使用化学计量的偶联剂、生产成本高等技术问题。
本发明提供了一种酰胺类化合物的合成方法,将具有式(I)结构的苄醇与具有式(II)结构的胺类化合物以有机溶剂作为媒介,在光催化剂负载金属P-C3N4存在的条件下经光催化反应制得具有式(III)结构的酰胺类化合物;
其中,式(I)结构的苄醇中,所述R3为C4~C20芳香基和杂环芳香基;式(II)结构的胺类化合物中,所述R1和R2各自独立地为H、C1~C20烷基、C3~C20环烷基、C2~C20烯烃基、C2~C20炔烃基、C6~C20芳香基,或R1、R2和与它们相连的N原子一起形成C1~C20杂环基;
所述烷基、环烷基、烯烃基、炔烃基、芳香基、杂环芳香基和杂环基的取代基可进一步任选地被卤素、羟基、氰基、硝基、烷氧基或芳香基单取代或相同或不同的多取代。
进一步地,所述R3为C4~C12芳香基或C4~C6杂环芳香基;所述R1和R2各自独立地为H、C1~C12烷基、C3~C12环烷基、C2~C12烯烃基、C2~C12炔烃基、C6~C12芳香基,或R1、R2和与它们相连的N原子一起形成C1~C6杂环基。
进一步地,所述R3为苯基、4-甲基苯基、4-甲氧基苯基、呋喃基、吡啶基、噻吩基;所述R1和R2各自独立地为H、甲基、乙基、丁基、辛烷基、十二烷基、环己基、苯基、或萘基,或R1、R2和与它们相连的N原子一起形成氮杂环庚-1-基或吡咯烷-1-基。
进一步地,所述苄醇和胺类化合物的摩尔比为1:1。
进一步地,所述有机溶剂为甲苯、四氢呋喃、二甲苯、苯和二氯甲烷中的一种或几种。
进一步地,所述光催化反应在碱存在或不存在的条件下进行,碱为叔丁醇钾、叔丁基醇钠、氢化钠、氢化钾、甲醇钠、乙醇钠、氢氧化钾、氢氧化钡、碳酸铯和碳酸钾中的一种或几种,所述苄醇和碱的摩尔比为1:0~3。
进一步地,所述负载金属P-C3N4中的负载金属为银、钌、钴、铜、铁、金、铂、钯、镨、锗、镍和锌中的一种或几种,负载金属P-C3N4的量为苄醇的0.1~5wt%。
更进一步的,所述负载金属P-C3N4的具体制备过程为:
(1)按三聚氰胺:水:70~99wt%浓磷酸的质量比为1:40~100:1.5~5,将三聚氰胺溶解于水中,加入浓磷酸,在120~200℃下晶化,过滤,干燥得到固体I;
(2)将固体I在400~550℃、N2氛围下焙烧2~8h,得到P-C3N4催化剂;
(3)将P-C3N4催化剂加入水中,加入负载金属的可溶性盐,控制P-C3N4与负载金属的质量比为1:0.01~0.5,水与P-C3N4的质量比为10:1~200:1;于30~80℃下真空干燥得到固体II;
(4)将固体II在200~550℃下焙烧0.5~6h,得到负载金属P-C3N4催化剂。
进一步地,所述合成方法的具体过程如下:
(1)将苄醇、胺类化合物、光催化剂负载金属P-C3N4、碱和有机溶剂投入至反应瓶中;
(2)15W~300W的光源下不断搅拌反应,得到酰胺类化合物。
进一步地,步骤(2)中,所述反应温度为室温,反应时间为60~600min。
与现有技术相比,本发明具备如下有益效果:
(1)光催化技术采用氧气或空气氧化具有温和的氧化性能,避免了使用过氧化物,更有利于催化剂的循环利用;
(2)过渡金属的负载非均相催化剂也有利于催化剂稳定性能的提升,这类催化剂只需简单的过滤就可从反应体系中分离出来,有效解决了均相催化剂与反应液难以分离的问题,而且催化剂可多次重复使用,催化活性损失不显著(见图9),降低了生产成本,符合绿色化学的要求;
(3)光催化剂在可见光辐射下,形成电子-空穴对,可以有效避免高温热反应,使产物的选择性更高。
附图说明
图1为实施例1中的吗啉-4-苯基-甲酮的核磁共振氢谱图;
图2为实施例1中的吗啉-4-苯基-甲酮的质谱图;
图3为实施例2中的苯基-吡咯烷-1-甲酮的核磁共振氢谱图;
图4为实施例2中的苯基-吡咯烷-1-甲酮的质谱图;
图5为实施例3中的正丁基苯甲酰胺的核磁共振氢谱图;
图6为实施例4中的N-环六亚甲基-1-苯基-甲酮核磁共振氢谱图;
图7为实施例4中的N-环六亚甲基-1-苯基-甲酮的质谱图;
图8为实施例5中的N,N-二丁基苯甲酰胺的质谱图;
图9为实施例1中的Ag/P-C3N4光催化剂的回收性能图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员所获得的所有其他实施例,都属于本发明保护的范围。除非另有定义,下文中所使用的所有专业术语与本领域技术人员通常理解的含义相同。本文中所使用的专业术语只是为了描述具体实施例的目的,并不是旨在限制本发明的保护范围。
实施例中所有份数和百分数除另有规定外均指质量。
实施例1
Ag/P-C3N4光催化剂的制备过程为:
(1)按三聚氰胺:水:浓磷酸的质量比为1:70:2,将三聚氰胺溶解于水中,加入浓磷酸,在160℃下晶化,过滤,干燥得到固体I;
(2)将固体I在520℃、N2氛围下焙烧5h,得到P-C3N4催化剂;
(3)将P-C3N4催化剂加入水中,加入AgNO3,控制P-C3N4与Ag的质量比为1:0.05,水与P-C3N4的质量比为20:1;于60℃下真空干燥得到固体II;
(4)将固体II在400℃下焙烧5h,得到Ag/P-C3N4光催化剂。
将2.7456g苯甲醇(含量为99%)加入100mL的反应瓶中,加入5mL甲苯作为溶剂,然后分批加入2.8571g叔丁基醇钾(含量为98%),加入2.2294g吗啡啉(含量为99%),再加入20mg Ag/P-C3N4,在常温、15W LED灯光照条件下反应4小时,得到灰白色固体。经分析检测,其中吗啉-4-苯基-甲酮含量为43.4%,基于苯甲醇的吗啉-4-苯基-甲酮的收率为92.7%。
Ag/P-C3N4光催化剂回收性能测试:经过滤、水洗后回收上述催化剂Ag/P-C3N4,于50℃下烘干,经重复使用6次,其催化效果并未明显减弱(见图9)。
白色固体物经柱层析法分离提纯后进行表征,其核磁共振氢谱如图1所示:δ2.50为溶剂峰,δ3.20~3.80(m,8H),δ7.46(m,2H),δ7.50(m,3H)其化学位移及氢的数目与吗啉-4-苯基-甲酮上的氢相符。
提纯后灰白色固体物的质谱如图2所示,谱图中质荷比为192.1076的峰是[M+1]离子峰,吗啉-4-苯基-甲酮理论分子量M为191.09,确认产物为吗啉-4-苯基-甲酮。
对比例1
将2.7456g苯甲醇(含量为99%)加入100mL的反应瓶中,加入5mL甲苯作为溶剂,然后分批加入2.8571g叔丁基醇钾(含量为98%),加入2.2294g吗啡啉(含量为99%),再加入6.5206gMnO2(含量为99%和叔丁基过氧化氢(含量70%)9.7363g。在常温、15W LED灯光照条件下反应10小时。经分析检测,未得到目标产物吗啉-4-苯基-甲酮。
实施例2
Ru/P-C3N4光催化剂的制备过程为:
(1)按三聚氰胺:水:浓磷酸的质量比为1:80:3,将三聚氰胺溶解于水中,加入浓磷酸,在170℃下晶化,过滤,干燥得到固体I;
(2)将固体I在550℃、N2氛围下焙烧4.5h,得到P-C3N4催化剂;
(3)将P-C3N4催化剂加入水中,加入RuCl3,控制P-C3N4与Ru的质量比为1:0.1,水与P-C3N4的质量比为40:1;于50℃下真空干燥得到固体II;
(4)将固体II在500℃下焙烧3.5h,得到Ru/P-C3N4光催化剂。
将2.7319g苯甲醇(含量为99%)加入100mL的反应瓶中,加入5mL甲苯作为溶剂,然后分两次加入共2.4515g叔丁醇钠(含量为98%),边加边适当振荡,待气泡消失后,加入1.7997g四氢吡咯(含量为99%),加入30mg Ru/P-C3N4,在常温、30W LED灯光照条件下反应6小时,得到浅棕色液体。经分析检测,其中苯基-吡咯烷-1-甲酮含量为38.4%,基于苯甲醇的苯基-吡咯烷-1-甲酮的收率为85.8%。
浅棕色液体物经柱层析法分离提纯后进行表征,其核磁共振氢谱如图3所示:
δ2.50为溶剂峰,δ1.82(m,4H),δ3.36(t,J=8Hz,2H),δ3.46(t,J=8Hz,2H),δ7.44(m,3H),δ7.48(m,2H),其化学位移及氢的数目与苯基-吡咯烷-1-甲酮的氢相符。
提纯浅棕色液体的质谱如图4所示,谱图中质荷比为176.1072的峰是[M+1]离子峰,苯基-吡咯烷-1-甲酮的理论分子量M为175.10,确认产物为苯苯基-吡咯烷-1-甲酮。
对比例2
将2.7456g苯甲醇(含量为99%)加入100mL的反应瓶中,加入5mL甲苯作为溶剂,然后分批加入2.8571g叔丁基醇钾(含量为98%),1.7997g四氢吡咯(含量为99%),再加入0.1000g RuCl3,在常温、30W LED灯光照条件下反应8小时。经分析检测,未得到目标产物苯基-吡咯烷-1-甲酮。
实施例3
Au/P-C3N4光催化剂的制备过程为:
(1)按三聚氰胺:水:浓磷酸的质量比为1:60:3,将三聚氰胺溶解于水中,加入浓磷酸,在150℃下晶化,过滤,干燥得到固体I;
(2)将固体I在480℃、N2氛围下焙烧6h,得到P-C3N4催化剂;
(3)将P-C3N4催化剂加入水中,加入氯化金,控制P-C3N4与Au的质量比为1:0.003,水与P-C3N4的质量比为70:1;于70℃下真空干燥得到固体II;
(4)将固体II在300℃下焙烧5h,得到Au/P-C3N4光催化剂。
将2.7322g苯甲醇(含量为99%)加入100mL的反应瓶中,加入5mL甲苯作为溶剂,然后分两次加入共1g氢化钠(含量为60%),边加边适当振荡,待气泡消失后,加入3.6973g正丁胺(含量为99%),加入15mg Au/P-C3N4,在常温、30W LED灯光照条件下反应6小时,得到浅黄色液体。经分析检测,其中正丁基苯甲酰胺含量为37.1%,基于苯甲醇的正丁基苯甲酰胺的收率为91.5%。
浅黄色液体物经柱层析法分离提纯后进行表征,其核磁共振氢谱如图5所示:
δ2.50为溶剂峰,δ0.85(t,J=8Hz,3H),δ1.80(m,4H),δ4.40(s,2H),δ7.15(m,1H),δ7.32(m,4H),其化学位移与正丁基苯甲酰胺上的氢相符。
对比例3
将2.7322g苯甲醇(含量为99%)加入100mL的反应瓶中,加入5mL甲苯作为溶剂,然后分两次加入共1g氢化钠(含量为60%),边加边适当振荡,待气泡消失后,加入3.6973g正丁胺(含量为99%),加入50mg AuCl3,加入含量70%的叔丁基过氧化氢9.7363g。在常温、30W LED灯光照条件下反应6小时,得到黑色液体。经分析检测,未得到正丁基苯甲酰胺。
实施例4
Pt/P-C3N4光催化剂的制备过程为:
(1)按三聚氰胺:水:浓磷酸的质量比为1:90:2.5,将三聚氰胺溶解于水中,加入浓磷酸,在150℃下晶化,过滤,干燥得到固体I;
(2)将固体I在500℃、N2氛围下焙烧5h,得到P-C3N4催化剂;
(3)将P-C3N4催化剂加入水中,加入氯化铂,控制P-C3N4与Pt的质量比为1:0.1,水与P-C3N4的质量比为25:1;于40℃下真空干燥得到固体II;
(4)将固体II在300℃下焙烧2.5h,得到Pt/P-C3N4光催化剂。
将2.7330g苯甲醇(含量为99%)加入100mL的反应瓶中,加入5mL甲苯作为溶剂,然后分两次加入共1g氢化钠(含量为60%),边加边适当振荡,待气泡消失后,加入2.5424g六亚甲基亚胺(含量为98%),加入25mg Pt/P-C3N4,在常温、100W LED灯光照条件下反应6小时,得到黄色液体。经分析检测,其中N-环六亚甲基-1-苯基-甲酮含量为33.8%,基于苯甲醇的N-环六亚甲基-1-苯基-甲酮的收率为86.4%。
黄色液体经柱层析法分离提纯后进行表征,其核磁共振氢谱如图6所示:
δ2.50为溶剂峰,δ1.52(s,4H),δ1.69(m,2H),δ3.25-3.35(t,J=8Hz,2H),δ3.55(t,J=8Hz,2H),δ4.50(d,J=8Hz,2H),δ7.31(m,3H),δ7.42(d,J=8Hz,2H)其化学位移及氢的数目与N-环六亚甲基-1-苯基-甲酮上的氢相符。
黄色液体经提纯后质谱如图7所示,其中质荷比为204.1388的峰是[M+1]离子峰,N-环六亚甲基-1-苯基-甲酮的理论分子量M为203.13,确认产物为N-环六亚甲基-1-苯基-甲酮。
实施例5
Cu/P-C3N4光催化剂的制备过程为:
(1)按三聚氰胺:水:浓磷酸的质量比为1:100:4,将三聚氰胺溶解于水中,加入浓磷酸,在180℃下晶化,过滤,干燥得到固体I;
(2)将固体I在550℃、N2氛围下焙烧2.5h,得到P-C3N4催化剂;
(3)将P-C3N4催化剂加入水中,加入CuCl2,控制P-C3N4与Cu的质量比为1:0.2,水与P-C3N4的质量比为35:1;于80℃下真空干燥得到固体II;
(4)将固体II在300℃下焙烧2h,得到Cu/P-C3N4光催化剂。
将2.7330g苯甲醇(含量为99%)加入100mL的反应瓶中,加入5mL甲苯作为溶剂,然后分两次加入共1g氢化钠(含量为60%),边加边适当振荡,待气泡消失后,加入3.2620g二正丁胺(含量为99%),加入10mg Cu/P-C3N4,在常温、100W LED灯光照条件下反应6小时,得到浅灰色液体。经分析检测,其中N,N-二丁基苯甲酰胺含量为34.6%,基于苯甲醇的N,N-二丁基苯甲酰胺的收率为76.8%。
浅灰色液体经提纯后的质谱如图8所示,其中质荷比为234.1858的峰是[M+1]离子峰,N,N-二丁基苯甲酰胺的理论分子量为233.18,确认产物为N,N-二丁基苯甲酰胺。
对比例4
将2.7456g苯甲醇(含量为99%)加入100mL的反应瓶中,加入5mL甲苯作为溶剂,然后分批加入2.8571g叔丁基醇钾(含量为98%),加入3.2620g二正丁胺(含量为99%),再加入0.1g CuCl2(含量为99%)和0.0500g哌啶醇氧化物(TEMPO,含量为98%),在常温、100WLED灯光照条件下反应10小时。经分析检测,未得到目标产物N,N-二丁基苯甲酰胺。
实施例6
将3.0510g4-甲基苯甲醇(含量为99%)加入100mL的反应瓶中,加入5mL甲苯作为溶剂,然后分批加入0.8g氢化钠(含量为60%),加入2.2294g吗啡啉(含量为99%),再加入20mg实施例1中制得的Ag/P-C3N4,在常温、30W LED灯光照条件下反应10小时。经分析检测,其中吗啉-4-甲苯基-甲酮含量为53.4%,基于苯甲醇的吗啉-4-甲苯基-甲酮的收率为72.6%。
实施例7
将3.4518g4-甲氧基苯甲醇(含量为99%)加入100mL的反应瓶中,加入5mL甲苯作为溶剂,然后分批加入0.8g氢化钠(含量为60%),加入2.2294g吗啡啉(含量为99%),再加入15mg实施例1中制得的Ag/P-C3N4,在常温、30W LED灯光照条件下反应6小时。经分析检测,其中吗啉-4-甲氧苯基-甲酮含量为56.2%,基于苯甲醇的吗啉-4-甲氧苯基-甲酮的收率为78.2%。
实施例8
将2.4513g糠醇(含量为99%)加入100mL的反应瓶中,加入5mL甲苯作为溶剂,然后分批加入0.8g氢化钠(含量为60%),加入2.2294g吗啡啉(含量为99%),再加入15mg实施例4中制得的Pt/P-C3N4,在常温、30W LED灯光照条件下反应6小时。经分析检测,其中呋喃-2-吗啉-4-甲酮含量为58.1%,基于苯甲醇的呋喃-2-吗啉-4-甲酮的收率为83.2%。
显然,上述实施例仅仅是为清楚地说明所作的举例,而并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (10)
2.根据权利要求1所述的酰胺类化合物的合成方法,其特征在于:所述R3为C4~C12芳香基或C4~C6杂环芳香基;所述R1和R2各自独立地为H、C1~C12烷基、C3~C12环烷基、C2~C12烯烃基、C2~C12炔烃基、C6~C12芳香基,或R1、R2和与它们相连的N原子一起形成C1~C6杂环基。
3.根据权利要求2所述的酰胺类化合物的合成方法,其特征在于:所述R3为苯基、4-甲基苯基、4-甲氧基苯基、呋喃基、吡啶基、噻吩基;所述R1和R2各自独立地为H、甲基、乙基、丁基、辛烷基、十二烷基、环己基、苯基、或萘基,或R1、R2和与它们相连的N原子一起形成氮杂环庚-1-基或吡咯烷-1-基。
4.根据权利要求1-3任一项所述的酰胺类化合物的合成方法,其特征在于:所述苄醇和胺类化合物的摩尔比为1:1。
5.根据权利要求1-3任一项所述的酰胺类化合物的合成方法,其特征在于:所述有机溶剂为甲苯、四氢呋喃、二甲苯、苯和二氯甲烷中的一种或几种。
6.根据权利要求4所述的酰胺类化合物的合成方法,其特征在于:所述光催化反应在碱存在或不存在的条件下进行,碱为叔丁醇钾、叔丁基醇钠、氢化钠、氢化钾、甲醇钠、乙醇钠、氢氧化钾、氢氧化钡、碳酸铯和碳酸钾中的一种或几种,所述苄醇和碱的摩尔比为1:0~3。
7.根据权利要求4任一项所述的酰胺类化合物的合成方法,其特征在于:所述负载金属P-C3N4中的负载金属为银、钌、钴、铜、铁、金、铂、钯、镨、锗、镍和锌中的一种或几种,负载金属P-C3N4的量为苄醇的0.1~5wt%。
8.根据权利要求7所述的酰胺类化合物的合成方法,其特征在于:所述负载金属P-C3N4的具体制备过程为:
(1)按三聚氰胺:水:70~99wt%浓磷酸的质量比为1:40~100:1.5~5,将三聚氰胺溶解于水中,加入浓磷酸,在120~200℃下晶化,过滤,干燥得到固体I;
(2)将固体I在400~550℃、N2氛围下焙烧2~8h,得到P-C3N4催化剂;
(3)将P-C3N4催化剂加入水中,加入负载金属的可溶性盐,控制P-C3N4与负载金属的质量比为1:0.01~0.5,水与P-C3N4的质量比为10:1~200:1;于30~80℃下真空干燥得到固体II;
(4)将固体II在200~550℃下焙烧0.5~6h,得到负载金属P-C3N4催化剂。
9.根据权利要求6所述的酰胺类化合物的合成方法,其特征在于,所述合成方法的具体过程如下:
(1)将苄醇、胺类化合物、光催化剂负载金属P-C3N4、碱和有机溶剂投入至反应瓶中;
(2)15W~300W的光源下不断搅拌反应,得到酰胺类化合物。
10.根据权利要求9所述的酰胺类化合物的合成方法,其特征在于:步骤(2)中,所述反应温度为室温,反应时间为60~600min。
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