CN115197069A - 一种醇类化合物取代胺化合成仲胺的方法 - Google Patents
一种醇类化合物取代胺化合成仲胺的方法 Download PDFInfo
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- CN115197069A CN115197069A CN202210805634.9A CN202210805634A CN115197069A CN 115197069 A CN115197069 A CN 115197069A CN 202210805634 A CN202210805634 A CN 202210805634A CN 115197069 A CN115197069 A CN 115197069A
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- -1 alcohol compound Chemical class 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000005576 amination reaction Methods 0.000 title claims abstract description 25
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 title abstract 7
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- 239000010955 niobium Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 36
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000001412 amines Chemical group 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 23
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 150000003335 secondary amines Chemical class 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- GAGSVOVTFFOFFX-UHFFFAOYSA-D [Nb+5].[Nb+5].OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O Chemical compound [Nb+5].[Nb+5].OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O GAGSVOVTFFOFFX-UHFFFAOYSA-D 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- LDPWMGUFXYRDRG-UHFFFAOYSA-I niobium(5+) pentaacetate Chemical compound [Nb+5].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O LDPWMGUFXYRDRG-UHFFFAOYSA-I 0.000 claims description 3
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- YJEJFHCHLNUCBH-UHFFFAOYSA-A 2-hydroxypropane-1,2,3-tricarboxylate niobium(5+) Chemical compound [Nb+5].[Nb+5].[Nb+5].OC(CC([O-])=O)(CC([O-])=O)C([O-])=O.OC(CC([O-])=O)(CC([O-])=O)C([O-])=O.OC(CC([O-])=O)(CC([O-])=O)C([O-])=O.OC(CC([O-])=O)(CC([O-])=O)C([O-])=O.OC(CC([O-])=O)(CC([O-])=O)C([O-])=O YJEJFHCHLNUCBH-UHFFFAOYSA-A 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 101100283604 Caenorhabditis elegans pigk-1 gene Proteins 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 2
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002821 niobium Chemical class 0.000 claims description 2
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 8
- 238000006467 substitution reaction Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 229910052697 platinum Inorganic materials 0.000 abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 abstract description 2
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract 2
- 239000012752 auxiliary agent Substances 0.000 abstract 2
- 229910052763 palladium Inorganic materials 0.000 abstract 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 238000007796 conventional method Methods 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 239000013067 intermediate product Substances 0.000 abstract 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 abstract 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 29
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 15
- 235000019445 benzyl alcohol Nutrition 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 8
- GTWJETSWSUWSEJ-UHFFFAOYSA-N n-benzylaniline Chemical compound C=1C=CC=CC=1CNC1=CC=CC=C1 GTWJETSWSUWSEJ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 150000003938 benzyl alcohols Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 description 1
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
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- 239000002841 Lewis acid Substances 0.000 description 1
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- 150000004753 Schiff bases Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
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- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 229940076131 gold trichloride Drugs 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/18—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及有机催化合成领域,公开了一种用于醇类化合物直接与有机胺进行取代胺化合成相应仲胺的铌(Nb)基催化剂及合成方法。通过本发明的催化剂和方法,能够以醇类化合物和有机胺为原料,在反应设备中发生取代胺化反应,得到高收率的仲胺。催化合成仲胺的传统方法主要有三种:1)通过借氢或还原催化胺化的方法,经中间产物醛酮合成仲胺,常用催化剂为铂、钯、钌等贵金属催化剂;2)通过取代胺化途径,利用三氟甲磺酸盐等制备的催化剂,并在助剂的作用下合成仲胺,或者利用三氯化铁等均相催化剂反应得到仲胺。与上面三种方法相比,该发明的方法为多相催化反应,不需要添加助剂,产物易分离,合成过程无污染,与铂、钯、钌等贵金属催化剂相比,催化剂成本低廉且稳定性好。
Description
技术领域
本发明涉及有机催化合成领域,尤其涉及一种用于醇类化合物直接与有机胺进行取代胺化合成相应仲胺的铌(Nb)基催化剂及合成方法。
背景技术
有机胺是合成化学中的一类重要中间体。在工业中,它们被普遍用做功能材料、农用化学品或精细化学品的组成成分。而其中的仲胺在表面活性剂、浮选剂、汽油清净剂、缓蚀剂、橡胶加工助剂、除草剂的乳化剂、纺织品柔软剂等领域有着广泛的应用。因此,开发用于合成仲胺的新催化方法引起大家关注,其中基于经典亲核取代的合成路线陆续被开发,如Buchwald−Hartwig胺化反应(F. Inoue, M. Kashihara, M. R. Yadav, Y. Nakao,Angew. Chem. Int. Ed. 2017, 56, 13307)。
有机胺的合成通常使用烷基卤化物等烷基化试剂,但由于卤化物的毒性和大量无机盐的产生,对环境并不友好。在2006年Prim课题组报道了使用金属路易斯酸金催化剂用于苄醇的直接胺化反应,该反应所使用的催化剂为三氯化金,使用二氯甲烷作为溶剂可以对一系列不同取代的苄醇进行磺酰胺化反应,而在这一反应中必须使用磺酰胺等具有弱酸性的胺源。随后在2012年中国科学家夏春谷教授发展了一种使用磺酸离子液体催化苄醇直接胺化的方法,该反应在1, 4-二氧六环为溶剂80 oC时可以获得二苯甲醇磺酰胺化产物。上述两种合成方法都需要用磺酸胺、酰胺等一系列具有弱酸性的有机胺作为胺源,而这些限制条件并不能满足在化工生产中的实际应用,因此发展一类非金属催化并且胺源为有机胺类化合物的醇胺化反应是非常有必要的。CN109053460B专利公开了一种利用非金属路易斯酸催化剂催化醇类化合物胺化的方法,其中将苄醇类化合物与苯胺类化合物混合,加入溶剂与催化剂三(五氟苯基)硼烷进行反应,该方法虽然也得到了胺类化合物,但所用的催化剂三(五氟苯基)硼烷含氟、制备复杂、易受潮。因此,亟需发展一种无污染、活性高的多相催化体系,来实现有机仲胺化合物的绿色高效合成。
发明内容
有鉴于此,本发明的目的在于提出一种将醇类化合物直接通过取代的方式进行胺化得到仲胺的铌基催化剂及合成方法,以解决现有技术中环境不友好、催化剂难分离或制备复杂等问题。
基于上述目的,本发明提供了一种用于醇类化合物一步取代胺化合成仲胺的方法,所述方法包括:以醇类化合物为原料,在多相铌基催化剂的作用下,进行胺化反应。
所述催化剂包括氧化铌、磷改性氧化铌、氮改性氧化铌、硫改性氧化铌、碳改性氧化铌催化剂中的一种或多种,优选磷改性氧化铌。铌基催化剂的制备可采用水热晶化法。制备铌基催化剂使用的铌源为草酸铌、醋酸铌、酒石酸铌中的一种或多种,优选酒石酸铌。改性铌基催化剂制备过程所使用的的改性剂为:磷改性所用的含磷试剂为磷酸盐(A3PO4)、磷酸氢盐(A2HPO4)、磷酸二氢盐(AH2PO4)中的一种或多种,A可以是K+、Na+、NH4+中的一种或多种;氮改性所用的含氮试剂为NH3、氨水、尿素、三聚氰胺中的一种或多种;硫改性所用的含硫试剂为硫酸盐(B2SO4)、硫酸氢盐(BHSO4)、亚硫酸盐(B2SO3)、亚硫酸氢盐(BHSO3)中的一种或多种,B可以是K+、Na+、NH4+中的一种或多种;碳改性所用的含碳试剂为糠醛、葡萄糖、苯酚、间苯二酚、邻苯二酚、对苯二酚中的一种或多种。
所述的胺化反应中,醇类化合物与催化剂的重量比为1:0.1-1:0.5,反应温度为100-220 ℃,反应时间为0.5-24小时,填充的氮气压力为0.1-2 Mpa,在有机溶剂中进行反应。其中醇类化合物包括含苯环的醇类或含双键的醇类化合物中的一种或几种;有机胺包括含苯环的胺类化合物中的一种或几种;有机溶剂可以是甲醇、乙醇、甲苯、异丙醇、乙二醇二甲醚、四氢呋喃、对二甲苯中的一种或几种,N源为含苯环的胺类及其相应胺类化合物。所述醇类化合物与溶剂的重量比为1:5-1:50。
所述反应可以是间歇式反应工艺,也可以是连续式反应工艺。间歇式反应工艺的反应器为间歇式反应釜;续式反应工艺的反应器为固定床、流化床中的一种。
根据文献报道,催化还原胺化是一种主要的合成胺方法,需要使用贵金属Ru、Pd、Pt等,或者非贵金属Co、Ni等的配合物。通过这种方法进行胺化反应,催化剂在反应一段时间后容易失活,并且该方法会生成部分希夫碱中间体,希夫碱容易加氢生成稳定的副产物,导致仲胺产物的收率降低。文献中也有报道通过取代反应进行胺化的方法,该方法利用酸性催化剂进行脱水而直接得到胺化产物,可避免副产物的产生,但其催化剂体系通常含有添加剂或助剂,或者使用均相催化剂、分离困难。或者,还有报道的取代胺化是通过生成醚中间体,再进行取代得到最终胺化产物的,其反应路径复杂。
本发明中,铌基催化剂中含有丰富的酸性位点,酸性位点可以活化醇类化合物中的羟基,使羟基基团容易被亲核取代基团通过SN1或SN2型机理直接进行取代,最终得到所需要的胺化产物。
因此,本发明的方法具有以下优势:1. 催化剂活性高,能够实现醇类化合物的取代胺化,得到高附加值的仲胺产物;2. 所用铌基催化剂为固体材料,与反应液易于分离并可循环使用,具有良好的工业应用前景;3. 铌基催化剂与贵金属催化剂相比,价格低廉,可以有效降低仲胺合成的工业化成本。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白,以下结合具体实施例,对本发明进一步详细说明,但还有许多其它实例。在阅读本发明之后,本领域的技术人员可对本发明进行各种等价形式的变形或修改,但这些变形或修改均属于本申请的权利要求所保护的范围。
实施例中使用的醇类化合物以苯甲醇为主,使用的胺类化合物为苯胺为主,但不仅限于两种底物,其中苯甲醇的转化率范围在40-100%,N-苄基苯胺的收率范围在15-99%。
以苯甲醇和苯胺为原料,在铌基催化剂作用下,进行取代胺化,制备N-苄基苯胺。间歇式反应釜的步骤如下:将0.4 g 苯甲醇,0.5g苯胺,0.1 g催化剂和5 ml溶剂加入到50ml的间歇式反应釜中,在氮气压力0.5-2 MPa,温度为100 oC-200 oC的条件下反应2-12小时。对反应产物进行气质联用色谱(GC-MS Agilent 7890A-5975C)定性分析和气相色谱(GCAgilent 7890A)定量分析,采用HP-5色谱柱,色谱柱的程序升温条件是:50 oC维持10mins,以5 oC/min 的升温速度升至250 oC,并在250 oC维持5 mins。
实施例1-5
对比不同晶化条件下制备的铌基催化剂在苯甲醇和苯胺制备N-甲基苯胺反应中的性能,包括以下步骤:
水热法:取20 g酒石酸铌,1 g磷酸二氢铵和20 ml去离子水加入到烧杯中搅拌溶解,随后转移到100 ml的聚四氟乙烯中进行晶化,经过滤、洗涤、干燥、焙烧后得到磷改性的氧化铌催化剂。
其中实施例1-5的不同晶化条件的铌基催化剂的性能评价条件为: 0.4 g苯甲醇,0.5 g苯胺,0.1 g铌基催化剂,5 ml对二甲苯,1 MPa氮气压力,140 oC,6 h;分析结果见表1(其中转化率指的是苯甲醇的转化率,收率指的是N-苄基苯胺的收率)。
实施例6-8
不同铌源制备的铌基催化剂在胺化反应中的性能评价:
按照实施例1-5中的水热法制备不同的铌基催化剂,晶化条件与实施例2相同,不同之处在于草酸铌、醋酸铌、柠檬酸铌代替了酒石酸铌。
其中实施例6-8的不同铌源制备的铌基催化剂的性能评价条件: 0.4 g苯甲醇,0.5 g苯胺,0.1 g铌基催化剂,5 ml对二甲苯,1 MPa氮气压力,140 oC,6 h;分析结果见表2(其中转化率指的是苯甲醇的转化率,收率指的是N-苄基苯胺的收率)。
实施例9-11
不同改性剂制备的铌基催化剂在胺化反应中的性能评价:
按照实施例1-5中的水热法制备不同改性剂的铌基催化剂,晶化条件与实施例2相同,不同之处在于NH3、硫酸氢钾、葡萄糖代替了磷酸二氢铵。
其中实施例9-11的不同改性剂制备的铌基催化剂的性能评价条件: 0.4 g苯甲醇,0.5 g苯胺,0.1 g铌基催化剂,5 ml对二甲苯,1 MPa氮气压力,140 oC,6 h;分析结果见表3(其中转化率指的是苯甲醇的转化率,收率指的是N-苄基苯胺的收率)。
实施例12-33
铌基催化剂在不同反应条件下的催化性能评价:使用的铌基催化剂与实施例2中催化剂的制备条件相同。
其中实施例12-33为0.1 g铌基催化剂在不同条件下进行胺化反应,其中醇与胺的摩尔比为1:1.5,溶剂为5 ml,分析结果见表4(其中转化率指的是醇的转化率,收率指的是仲胺产物的收率)。
实施例34-41
铌基催化剂在固定床反应器中胺化反应的性能评价:
按照实施例1-5中的水热法在不同晶化时间和晶化温度的条件下制备不同晶化条件的铌基催化剂。
不同晶化条件的铌基催化剂在连续式固定床中的性能评价条件:0.1 g催化剂,苯甲醇的进料空速为30 h-1,氮气流速为30 ml/h,氮气压力为1 MPa,温度为140 oC;分析结果见表5(其中转化率指的是苯甲醇的转化率,收率指的是N-苄基苯胺的收率)。
Claims (8)
1.一种用于醇类和有机胺化合物合成仲胺的铌(Nb)基催化剂及方法,其特征在于,所述方法包括:以醇类和有机胺化合物为原料,在铌基催化剂的作用下,在溶剂存在条件下进行胺化反应,醇类化合物的转化率>99%,胺化反应生成相应的仲胺产物收率为72%。
2.根据权利要求1所述的方法,所述铌基催化剂包括氧化铌、磷改性氧化铌、氮改性氧化铌、硫改性氧化铌、碳改性氧化铌催化剂中的一种或多种,优选磷改性氧化铌。
3.根据权利要求1所述的方法,铌基催化剂的制备可采用水热晶化法,水热晶化温度在140-200 oC下进行,优选150-180 oC;晶化时间12-72小时,优选20-30小时。
4.根据权利要求3所述的方法,制备铌基催化剂使用的铌源为草酸铌、醋酸铌、酒石酸铌、柠檬酸铌中的一种或多种,优选酒石酸铌。
5.根据权利要求3所述的方法,改性铌基催化剂制备过程所使用的的改性剂为:磷改性所用的含磷试剂为磷酸盐(A3PO4)、磷酸氢盐(A2HPO4)、磷酸二氢盐(AH2PO4)中的一种或多种,A可以是K+、Na+、NH4+中的一种或多种;氮改性所用的含氮试剂为NH3、氨水、尿素、三聚氰胺中的一种或多种;硫改性所用的含硫试剂为硫酸盐(B2SO4)、硫酸氢盐(BHSO4)、亚硫酸盐(B2SO3)、亚硫酸氢盐(BHSO3)中的一种或多种,B可以是K+、Na+、NH4+中的一种或多种;碳改性所用的含碳试剂为糠醛、葡萄糖、苯酚、间苯二酚、邻苯二酚、对苯二酚中的一种或多种。
6.根据权利要求1,胺化反应的方法,其特征在:
所述醇类化合物包括含苯环的醇类或含双键的醇类化合物中的一种或几种;有机胺包括含苯环的胺类化合物中的一种或几种;
和,所述醇类化合物与催化剂的重量比为1:0.1-1:0.5;
和,所述反应温度为100 ℃-220 ℃,优选地,所述反应温度为120 ℃-180 ℃;
和,所述反应时间0.5-24小时,优选地,所述反应时间为2-20小时;
和,所述填充氮气压力为0.1 MPa-2 MPa,,优选地,所述填充氮气的压力为0.5 MPa-1.2 MPa。
7.根据权利要求1所述的方法,其中,溶剂为甲醇、乙醇、甲苯、异丙醇、乙二醇二甲醚、四氢呋喃、对二甲苯中的一种或几种,优选甲苯、对二甲苯中的一种或两种;所述醇类化合物与溶剂的重量比为1:5-1:50,优选地,醇类化合物与溶剂的重量比为1:10-1:25。
8.根据权利要求1所述的方法,其中,所述反应可以是间歇式反应工艺,也可以是连续式反应工艺;间歇式反应工艺的反应器为间歇式反应釜;连续式反应工艺的反应器为固定床、流化床中的一种。
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