KR102622005B1 - The Method of Producing Aromatic Compound Comprising Pyridin Group - Google Patents
The Method of Producing Aromatic Compound Comprising Pyridin Group Download PDFInfo
- Publication number
- KR102622005B1 KR102622005B1 KR1020190001272A KR20190001272A KR102622005B1 KR 102622005 B1 KR102622005 B1 KR 102622005B1 KR 1020190001272 A KR1020190001272 A KR 1020190001272A KR 20190001272 A KR20190001272 A KR 20190001272A KR 102622005 B1 KR102622005 B1 KR 102622005B1
- Authority
- KR
- South Korea
- Prior art keywords
- reaction
- group
- compound
- scheme
- hydrogen
- Prior art date
Links
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 88
- 239000001257 hydrogen Substances 0.000 claims abstract description 88
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 150000003222 pyridines Chemical class 0.000 claims abstract description 13
- 238000005658 halogenation reaction Methods 0.000 claims abstract description 11
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 81
- 125000004432 carbon atom Chemical group C* 0.000 claims description 50
- 125000001424 substituent group Chemical group 0.000 claims description 35
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 238000005804 alkylation reaction Methods 0.000 claims description 11
- -1 methylene, ethylene, propylene Chemical group 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 3
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 claims description 3
- HRADVHZVMOMEPU-UHFFFAOYSA-N 3-iodopyrrolidine-2,5-dione Chemical compound IC1CC(=O)NC1=O HRADVHZVMOMEPU-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- FFHWGQQFANVOHV-UHFFFAOYSA-N dimethyldioxirane Chemical compound CC1(C)OO1 FFHWGQQFANVOHV-UHFFFAOYSA-N 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 3
- 229950009390 symclosene Drugs 0.000 claims description 3
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims 1
- 230000026030 halogenation Effects 0.000 claims 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 79
- 239000011232 storage material Substances 0.000 abstract description 13
- 238000002485 combustion reaction Methods 0.000 abstract description 6
- 239000000446 fuel Substances 0.000 abstract description 6
- 125000003118 aryl group Chemical group 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 21
- 238000003860 storage Methods 0.000 description 21
- 238000006356 dehydrogenation reaction Methods 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 13
- 239000000376 reactant Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 150000002431 hydrogen Chemical class 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 229910052707 ruthenium Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 125000005842 heteroatom Chemical group 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 125000001072 heteroaryl group Chemical group 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- NJWIMFZLESWFIM-UHFFFAOYSA-N 2-(chloromethyl)pyridine Chemical compound ClCC1=CC=CC=N1 NJWIMFZLESWFIM-UHFFFAOYSA-N 0.000 description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- CFZKDDTWZYUZKS-UHFFFAOYSA-N picoline N-oxide Chemical compound CC1=CC=CC=[N+]1[O-] CFZKDDTWZYUZKS-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 101100137555 Mus musculus Prg2 gene Proteins 0.000 description 3
- 229910020667 PBr3 Inorganic materials 0.000 description 3
- 125000005103 alkyl silyl group Chemical group 0.000 description 3
- 125000005104 aryl silyl group Chemical group 0.000 description 3
- 125000004104 aryloxy group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- IPNPIHIZVLFAFP-UHFFFAOYSA-N phosphorus tribromide Chemical compound BrP(Br)Br IPNPIHIZVLFAFP-UHFFFAOYSA-N 0.000 description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000002993 cycloalkylene group Chemical group 0.000 description 2
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 125000004404 heteroalkyl group Chemical group 0.000 description 2
- 125000004446 heteroarylalkyl group Chemical group 0.000 description 2
- 125000005241 heteroarylamino group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- SHNUBALDGXWUJI-UHFFFAOYSA-N pyridin-2-ylmethanol Chemical compound OCC1=CC=CC=N1 SHNUBALDGXWUJI-UHFFFAOYSA-N 0.000 description 2
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical class [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OIAQMFOKAXHPNH-UHFFFAOYSA-N 1,2-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1 OIAQMFOKAXHPNH-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical group C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FUUPYXUBNPJSOA-UHFFFAOYSA-N 9-ethyl-1,2,3,4,4a,4b,5,6,7,8,8a,9a-dodecahydrocarbazole Chemical compound C12CCCCC2N(CC)C2C1CCCC2 FUUPYXUBNPJSOA-UHFFFAOYSA-N 0.000 description 1
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019201 POBr3 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminum chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000002676 chrysenyl group Chemical group C1(=CC=CC=2C3=CC=C4C=CC=CC4=C3C=CC12)* 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 150000001975 deuterium Chemical group 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000007345 electrophilic aromatic substitution reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 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
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 125000005597 hydrazone group Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/127—Preparation from compounds containing pyridine rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
본 발명은 연료전지와 수소 연소 장치 등의 수소를 이용하는 장치에 수소를 공급하기 위한 수소 저장(Hydrogen Storage) 물질로 사용 가능한 피리딘 그룹을 포함하는 방향족 화합물을 제조하는 방법에 관한 것으로, 보다 상세하게는 피리딘 유도체의 산화 반응, 할로겐화 반응 및 프리델 크라프트(Friedel-Craft) 반응을 이용하여 피리딘 그룹을 포함하는 방향족 화합물을 제조하는 방법에 관한 것이다.The present invention relates to a method of producing an aromatic compound containing a pyridine group that can be used as a hydrogen storage material to supply hydrogen to devices that use hydrogen such as fuel cells and hydrogen combustion devices, and more specifically, It relates to a method of producing an aromatic compound containing a pyridine group using the oxidation reaction, halogenation reaction, and Friedel-Craft reaction of a pyridine derivative.
Description
본 발명은 연료전지와 수소 연소 장치 등의 수소를 이용하는 장치에 수소를 공급하기 위한 수소 저장(Hydrogen Storage) 물질로 사용 가능한, 피리딘 그룹을 포함하는 방향족 화합물의 신규한 제조방법에 관한 것이다.The present invention relates to a novel manufacturing method of an aromatic compound containing a pyridine group that can be used as a hydrogen storage material to supply hydrogen to devices that use hydrogen, such as fuel cells and hydrogen combustion devices.
화석 에너지의 고갈 및 환경 오염 문제로 인하여 신재생 대체 에너지에 대한 요구가 크며, 이에 대한 대체 에너지의 하나로서 수소가 주목받고 있다. 특히 연료전지와 수소 연소 장치의 경우 수소를 반응 가스로 사용하고 있는데, 연료전지와 수소 연소 장치를 예컨대 자동차나 각종 전자 제품 등에 응용하기 위해서는 수소의 안정적이고 지속적인 공급 기술이 요구된다.Due to the depletion of fossil energy and environmental pollution problems, there is a great demand for new and renewable alternative energy, and hydrogen is attracting attention as one of the alternative energies. In particular, fuel cells and hydrogen combustion devices use hydrogen as a reaction gas, and in order to apply fuel cells and hydrogen combustion devices to automobiles and various electronic products, for example, a stable and continuous supply technology for hydrogen is required.
수소를 이용하는 장치에 있어서 수소를 공급하기 위해서는 별도로 설치된 수소 저장 장치 (수소 공급 장치)로부터 수소가 필요할 때마다 수소를 공급받는 방식을 사용할 수 있다. 대표적인 예로는 압축수소저장 및 액화수소저장 방법이 있는데, 이들 기술은 수소 생산처로부터 수소 수요처까지 수소를 이송하는데 가격 및 안전에 대한 이슈가 있을 수 있다.To supply hydrogen in a device using hydrogen, a method can be used in which hydrogen is supplied from a separately installed hydrogen storage device (hydrogen supply device) whenever hydrogen is needed. Representative examples include compressed hydrogen storage and liquefied hydrogen storage. These technologies transport hydrogen from hydrogen producers to hydrogen consumers, but there may be issues regarding price and safety.
예를 들어, 수소는 최대 875 bar의 압력에서 저장하기에 적합한 고압 탱크에 압축된 형태로 저장될 수 있다. 또한 적합한 극저온 용기, 바람직하게는 초절연(superinsulated)된 극저온 용기에 저온 액화 수소의 저장이 공지되어 있다. For example, hydrogen can be stored in compressed form in high-pressure tanks suitable for storage at pressures of up to 875 bar. It is also known to store cold liquefied hydrogen in suitable cryogenic vessels, preferably superinsulated cryogenic vessels.
이외에, 수소를 저장하고 발생시키는 물질을 수소 이용 장치에 탑재하여, 해당 물질을 반응 시켜 수소를 발생시키고, 이를 공급하는 방식을 사용할 수 있다. 이 방식에는 예컨대, 금속수소화물(metal hydride) 이용 방법, 흡착, 탈착/탄소 (absorbents/carbon) 이용 방법, 화학적 수소저장 방법(chemical hydrogen storage) 등이 제안되고 있으며, 암모니아 보레인, 실란 화합물, 개미산 등과 같은 다양한 화학수소화물을 이용한 수소저장 기술이 연구되고 있다.In addition, a method of loading a material that stores and generates hydrogen into a hydrogen utilization device, reacting the material to generate hydrogen, and supplying the hydrogen can be used. For this method, for example, methods using metal hydride, adsorption, desorption/carbon (absorbents/carbon) methods, and chemical hydrogen storage methods are proposed, and ammonia borane, silane compounds, Hydrogen storage technology using various chemical hydrides such as formic acid is being studied.
이와 더불어, 최근에는 가역성이 용이한 유기화합물을 이용한 수소저장기술이 활발하게 이루어지고 있는데, 예로, 일본에서는 경제적 수소 이송을 고려하여 톨루엔 기반의 수소저장기술이 연계된 수소 발전소를 구축하고 있으며, 독일에서는 디벤질 톨루엔 계열의 화합물을 기반으로 하여 가역적 수소저장 특성을 규명하고자 하고 있다. In addition, hydrogen storage technology using easily reversible organic compounds has been actively developed in recent years. For example, Japan is building a hydrogen power plant with toluene-based hydrogen storage technology in consideration of economical hydrogen transport, and Germany is building a hydrogen storage technology using toluene-based hydrogen storage technology. is attempting to identify reversible hydrogen storage characteristics based on dibenzyl toluene series compounds.
상기에서 언급한 화합물을 기반으로 하는 가역적 수소저장기술은 실험적 단계에 있는 것으로, 수소와 화학적으로 결합할 수 있는 수소화(hydrogenation)가 가능한 유기 화합물에서 수소의 저장이 이루어진다. Reversible hydrogen storage technology based on the compounds mentioned above is in the experimental stage, and hydrogen is stored in hydrogenated organic compounds that can chemically combine with hydrogen.
구체적으로 에너지가 부족한 물질(A)에 수소를 로딩하여 에너지가 풍부한 물질(B)을 형성하며, 에너지 로딩 작업은 전형적으로 초대기압 압력(superatmospheric pressure) 하에 촉매 수소화 반응의 종래 기술의 형태를 취한다. 물질(B)은 저압과 고온에서 촉매 수소화에 의해 에너지가 언로딩된다. 공정에서 다시 방출된 수소는, 예를 들어, 연료 전지 또는 연소 엔진에서 에너지 공급원으로 유용하다. 에너지가 부족한 형태(A)는 이 경우 에너지가 풍부한 시간에 에너지가 풍부한 장소에서 수소로 재로딩될 수 있도록 액체로 저장되고 운송될 수 있다. 이러한 유형의 시스템은 액체 유기 수소 운반체(liquid organic hydrogen carriers, LOHCs)로 알려져 있다. Specifically, hydrogen is loaded into an energy-poor material (A) to form an energy-rich material (B), and the energy loading operation typically takes the form of a prior art catalytic hydrogenation reaction under superatmospheric pressure. . Material (B) is unloaded with energy by catalytic hydrogenation at low pressure and high temperature. The hydrogen released again in the process is useful as an energy source, for example in fuel cells or combustion engines. The energy-poor form (A), in this case, can be stored and transported as a liquid so that it can be reloaded with hydrogen at an energy-rich location at an energy-rich time. These types of systems are known as liquid organic hydrogen carriers (LOHCs).
종래 기술 LOHC 시스템은 물질 쌍(substance pairs)인 것이 바람직하고, 여기서, 에너지가 부족한 물질(A)은 에너지 로딩 단계에서 수소화된 끓는 점이 높은 작용기화 방향족 화합물이다. 개시되어 있는 한 가지 특히 바람직한 예는 물질 쌍 N-에틸카바졸/퍼히드로-N-에틸카바졸을 사용하는 것에 관한 것으로, 이는 전형적으로 약 140℃ 및 높은 압력에서 에너지 로딩을 허용하고 230℃ 내지 250℃의 온도에서 에너지 언로딩(energy unloading)을 허용한다. 에너지가 풍부한 물질인 퍼히드로-N-에틸카바졸은 언급된 시스템에서 수소의 질량 기준으로 약 5.8%의 수소 용량(hydrogen capacity)을 갖는다.Prior art LOHC systems are preferably substance pairs, where the energy-deficient substance (A) is a high boiling functionalized aromatic compound that is hydrogenated in the energy loading step. One particularly preferred example disclosed relates to the use of the material pair N-ethylcarbazole/perhydro-N-ethylcarbazole, which typically allows energy loading at about 140° C. and high pressures and has a temperature range of 230° C. to 230° C. Energy unloading is allowed at a temperature of 250°C. Perhydro-N-ethylcarbazole, an energy-rich material, has a hydrogen capacity of about 5.8% by mass of hydrogen in the mentioned system.
이와 관련된 종래기술로서, 한국등록특허 제10-1845515호(공고일: 2018.04.04)에서는 액상 수소저장물질로서, 1,1'-바이페닐과 1,1'-메틸렌다이벤젠을 1:1.8 내지 1:2.5의 중량비율로 포함하는 액상 수소저장물질을 제시하였으며, 또한 한국등록특허 제10-1862012호(공개일: 2018.03.19)에서는 피리딘계 수소저장물질을 활용한 수소 저장 및 방출 시스템에서 피리딘계 수소저장물질을 합성함에 있어서 2-피리딘메탄올을 출발물질로 사용하여 합성한 제조예가 개재되어 있다.As a related prior art, Korea Patent No. 10-1845515 (announcement date: 2018.04.04) uses 1,1'-biphenyl and 1,1'-methylenedibenzene at a ratio of 1:1.8 to 1 as a liquid hydrogen storage material. A liquid hydrogen storage material containing a weight ratio of :2.5 was presented, and in Korea Patent No. 10-1862012 (publication date: 2018.03.19), a pyridine-based hydrogen storage and release system using a pyridine-based hydrogen storage material was proposed. In synthesizing a hydrogen storage material, a production example using 2-pyridinemethanol as a starting material is provided.
그러나 상기 제조예에서 출발물질로 사용된 2-피리딘메탄올보다 낮은 단가를 가지는 피리딘계 유도체를 출발물질로 사용하여 수소저장물질을 합성하는 방법의 개발을 통해서 수소저장물질의 생산단가를 낮출 수 있을 것으로 기대된다.However, it is expected that the production cost of the hydrogen storage material can be lowered through the development of a method of synthesizing the hydrogen storage material using a pyridine-based derivative with a lower cost than 2-pyridine methanol used as the starting material in the above production example. It is expected.
따라서 현재까지는 이러한 불포화고리를 포함하는 수소저장물질을 합성하기 위한 기술개발이 개선의 여지가 있으며, 이에 본 발명자는 피리딘 그룹을 포함하는 방향족 화합물이 상기 연료전지와 수소 연소 장치 등의 수소를 이용하는 장치에 수소를 공급하기 위한 수소 저장(Hydrogen Storage) 물질로서 사용할 수 있음을 알았으며, 또한 상기 피리딘 그룹을 포함하는 방향족 화합물의 신규한 제조방법을 확인하고 본 발명을 완성하였다. Therefore, there is room for improvement in the development of technology to synthesize hydrogen storage materials containing such unsaturated rings, and the present inventors have proposed that aromatic compounds containing pyridine groups be used in devices that use hydrogen such as fuel cells and hydrogen combustion devices. It was found that it can be used as a hydrogen storage material for supplying hydrogen to , and a new method for producing an aromatic compound containing the pyridine group was confirmed and the present invention was completed.
본 발명은 전술한 문제점을 해결하기 위한 것으로서, LOHC 시스템에서 사용가능한 N-헤테로아릴을 포함하는 방향족 화합물의 제조를 위한 신규한 제조방법을 제시한다.The present invention is intended to solve the above-mentioned problems and proposes a novel production method for producing an aromatic compound containing N-heteroaryl that can be used in the LOHC system.
상기 기술적 과제를 달성하기 위하여, 본 발명은 a) 하기 [반응식 1]내, 화합물 a로 표시되는 피리딘 유도체의 산화 반응으로부터 화합물 b로 표시되는 화합물을 제조하는 단계; b) 하기 [반응식 2]내, 화합물 b로 표시되는 화합물내 치환기 -R1-H의 할로겐화 반응으로부터 화합물 c로 표시되는 화합물을 제조하는 단계; 및 c) 하기 [반응식 3]내, 화합물 c로 표시되는 화합물과 화합물 d로 표시되는 화합물의 알킬화 반응으로부터 화합물 e로 표시되는 화합물을 제조하는 단계;를 포함하는, 피리딘 그룹을 포함하는 방향족 화합물을 제조하는 방법을 제공한다.In order to achieve the above technical problem, the present invention includes the steps of a) preparing a compound represented by compound b from the oxidation reaction of a pyridine derivative represented by compound a in the following [Scheme 1]; b) preparing a compound represented by compound c from the halogenation reaction of the substituent -R1-H in the compound represented by compound b in the following [Scheme 2]; and c) preparing a compound represented by compound e from an alkylation reaction of a compound represented by compound c and a compound represented by compound d in [Scheme 3] below; an aromatic compound containing a pyridine group, including: Provides a manufacturing method.
[반응식 1] [Scheme 1]
[반응식 2] [Scheme 2]
[반응식 3] [Scheme 3]
상기 [반응식 1] 내지 [반응식 3]에서,In [Reaction Scheme 1] to [Reaction Scheme 3],
상기 X는 F, Cl, Br, I 로부터 선택되는 어느 하나의 할로겐이며,X is any halogen selected from F, Cl, Br, and I,
상기 치환기 R1는 치환 또는 비치환된 탄소수 1 내지 30의 알킬렌기또는 치환 또는 비치환된 탄소수 3 내지 30의 시클로알킬렌기이며, The substituent R 1 is a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms or a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms,
상기 치환기 R2는 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 6 내지 50의 아릴기, 치환 또는 비치환된 탄소수 3 내지 30의 시클로알킬기, 치환 또는 비치환되고 이종 원자로 O, N, S 및 Si에서 선택되는 1 내지 3의 헤테로원자를 갖는 탄소수 2 내지 50의 헤테로아릴기, 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴옥시기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴실릴기 중에서 선택되는 어느하나이다.The substituent R 2 is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, or a substituted or unsubstituted heteroatom. A heteroaryl group of 2 to 50 carbon atoms having 1 to 3 heteroatoms selected from O, N, S and Si, a substituted or unsubstituted alkoxy group of 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group of 6 to 30 carbon atoms It is any one selected from an aryloxy group, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms.
일 실시예로서, 상기 [반응식 1] 내지 [반응식 3]에서 상기 치환기 R1는 메틸렌기일 수 있다.As an example, in [Scheme 1] to [Scheme 3], the substituent R 1 may be a methylene group.
일 실시예로서, 상기 [반응식 3]에서 상기 치환기 R2는 치환 또는 비치환된 탄소수 1 내지 30의 알킬기일 수 있다.As an example, in [Scheme 3], the substituent R 2 may be a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.
일 실시예로서, 상기 [반응식 3]에서 상기 치환기 R2는 메틸기일 수 있다.As an example, in [Scheme 3], the substituent R 2 may be a methyl group.
일 실시예로서, 상기 a)단계에서의 화합물 a로 표시되는 피리딘 유도체의 산화 반응은 산소, 과산화수소(H2O2), 메타클로로퍼벤조익에시드(m-chloro perbenzoic acid,mCPBA), 디메틸디옥시렌(Dimethyldioxirane) 중에서 선택되는 어느 하나 또는 이들의 혼합물을 이용할 수 있다.As an example, the oxidation reaction of the pyridine derivative represented by compound a in step a) is carried out using oxygen, hydrogen peroxide (H 2 O 2 ), m -chloro perbenzoic acid (mCPBA), and dimethyl dimethyl chloride. Any one selected from oxirene (dimethyldioxirane) or a mixture thereof may be used.
일 실시예로서, 상기 a)단계에서의 산화 반응의 반응조건은 30~150 ℃, 1~30 시간의 반응시간일 수 있다.As an example, the reaction conditions for the oxidation reaction in step a) may be 30 to 150° C. and a reaction time of 1 to 30 hours.
일 실시예로서, 상기 b)단계에서의 할로겐화 반응은 치환기 -R1-H의 말단 탄소를 PCl3, PBr3, POCl3 , 트리클로로이소시아누릭산(trichloroisocyanuric acid), HBr, Bromosucciniminde, I2, Iodosuccinimide, Trifluoromethanesulfonimide 중에서 선택되는 어느 하나 또는 이들의 혼합물을 사용할 수 있다.As an example, the halogenation reaction in step b) replaces the terminal carbon of the substituent -R1-H with PCl3, PBr3, POCl 3 , trichloroisocyanuric acid, HBr, Bromosucciniminde, I 2 , Iodosuccinimide, Trifluoromethanesulfonimide. Any one selected from among them or a mixture thereof may be used.
일 실시예로서, 상기 c)단계에서 알킬화 반응은 프리델 크라프트(Friedel-Craft) 반응일 수 있다.As an example, the alkylation reaction in step c) may be a Friedel-Craft reaction.
일 실시예로서, 상기 단계 c)에서 알킬화 반응의 반응조건은 30~150 ℃이며, 1~30 시간의 반응시간일 수 있다.As an example, the reaction conditions for the alkylation reaction in step c) may be 30 to 150° C. and the reaction time may be 1 to 30 hours.
본 발명은 피리딘 그룹을 포함하는 방향족 화합물의 신규한 제조방법을 제공할 수 있으며, 피리딘을 출발물질로 하여, 값싼 원재료를 사용하면서도, 3단계 공정만으로 피리딘 그룹에 방향족 고리가 연결된 화합물을 경제적이며 고수율을 보여주는 신규한 제조방법을 제공할 수 있다.The present invention can provide a new method for producing an aromatic compound containing a pyridine group, and using pyridine as a starting material, a compound in which an aromatic ring is connected to a pyridine group can be produced economically and efficiently using only a three-step process while using inexpensive raw materials. A new manufacturing method that shows yield can be provided.
도 1은 디시클로헥실메탄(dicyclohexylmethane)에 대한 N-치환 및 메틸기(CH3) 첨가 효과에 따른 계산된 탈수소화 엔탈피 값과 이론 수소 저장 용량이다. (괄호 안의 값은 각 화살표의 분자 사이의 탈수소화 엔탈피 값의 차이를 나타낸다.)
도 2는 Pd/C 촉매를 사용하여 H12-MBP과 Pt/C 촉매를 사용하여 H12-BT을 a) 230, 250 및 270 ℃ 각각의 온도에서 M/R = 1 mol% 일 때 탈수소화 반응시 산소 발생을 시간에 따라 도시한 그래프이며, b) 230 ℃에서 M/R = 4 mol%일 때와 M/R = 6 mol %일 때의 탈수소화 반응시 산소 발생을 시간에 따라 도시한 그래프이다.Figure 1 shows the calculated dehydrogenation enthalpy value and theoretical hydrogen storage capacity according to the effect of N-substitution and addition of a methyl group (CH 3 ) to dicyclohexylmethane. (The values in parentheses represent the difference in dehydrogenation enthalpy values between the molecules of each arrow.)
Figure 2 shows a) dehydrogenation of H 12 -MBP using a Pd/C catalyst and H 12 -BT using a Pt/C catalyst when M/R = 1 mol% at each temperature of 230, 250, and 270 °C. This is a graph showing the oxygen evolution over time during the reaction, and b) the oxygen evolution over time during the dehydrogenation reaction at 230°C when M/R = 4 mol% and M/R = 6 mol%. It's a graph.
다른 식으로 정의히지 않는 한, 본 명세서에서 사용된 모든 기술적 및 과학적 용어들은 본 발명이 속하는 기술분야에서 숙련된 전문가에 의해서 통상적으로 이해되는 것과 동일한 의미를 가진다. 일반적으로, 본 명세서에서 사용된 명명법은 본 기술분야에서 잘 알려져 있고 통상적으로 사용되는 것이다.Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. In general, the nomenclature used herein is well known and commonly used in the art.
본원 명세서 전체에서, 어떤 부분이 어떤 구성 요소를 "포함"한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성 요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다.Throughout the specification of the present application, when a part "includes" a certain component, this means that it may further include other components rather than excluding other components unless specifically stated to the contrary.
본 명세서에서, "액상"이란 액체 상태를 의미한다.In this specification, “liquid phase” means liquid state.
본 명세서에서, "수소 저장 물질"이란 수소(H) 원자를 포함하는 물질과 반응하여 수소원자를 화학결합을 통해 저장하고, 일정에너지가 가해지는 경우 수소(H2)를 가역적으로 방출할 수 있는 물질을 의미한다.In this specification, “hydrogen storage material” refers to a material that reacts with a material containing hydrogen (H) atoms, stores hydrogen atoms through chemical bonds, and reversibly releases hydrogen (H2) when a certain amount of energy is applied. means.
본 명세서에서, "옥사이드"는 =O 기를 의미한다.As used herein, “oxide” refers to the =O group.
본 발명은 a) 하기 [반응식 1]내, 화합물 a로 표시되는 피리딘 유도체의 산화 반응으로부터 화합물 b로 표시되는 화합물을 제조하는 단계; b) 하기 [반응식 2]내, 화합물 b로 표시되는 화합물내 치환기 -R1-H의 할로겐화 반응으로부터 화합물 c로 표시되는 화합물을 제조하는 단계; 및 c) 하기 [반응식 3]내, 화합물 c로 표시되는 화합물과 화합물 d로 표시되는 화합물의 알킬화 반응으로부터 화합물 e로 표시되는 화합물을 제조하는 단계;를 포함하는, 피리딘 그룹을 포함하는 방향족 화합물을 제조하는 방법을 제공한다.The present invention includes the steps of a) preparing a compound represented by compound b from the oxidation reaction of a pyridine derivative represented by compound a in the following [Scheme 1]; b) preparing a compound represented by compound c from the halogenation reaction of the substituent -R1-H in the compound represented by compound b in the following [Scheme 2]; and c) preparing a compound represented by compound e from an alkylation reaction of a compound represented by compound c and a compound represented by compound d in [Scheme 3] below; an aromatic compound containing a pyridine group, including: Provides a manufacturing method.
[반응식 1] [Scheme 1]
[반응식 2] [Scheme 2]
[반응식 3] [Scheme 3]
상기 [반응식 1] 내지 [반응식 3]에서,In [Reaction Scheme 1] to [Reaction Scheme 3],
상기 X는 F, Cl, Br, I 로부터 선택되는 어느 하나의 할로겐이며,X is any halogen selected from F, Cl, Br, and I,
상기 치환기 R1는 치환 또는 비치환된 탄소수 1 내지 30의 알킬렌기또는 치환 또는 비치환된 탄소수 3 내지 30의 시클로알킬렌기이며, The substituent R 1 is a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms or a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms,
상기 치환기 R2는 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 6 내지 50의 아릴기, 치환 또는 비치환된 탄소수 3 내지 30의 시클로알킬기, 치환 또는 비치환되고 이종 원자로 O, N, S 및 Si에서 선택되는 1 내지 3의 헤테로원자를 갖는 탄소수 2 내지 50의 헤테로아릴기, 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴옥시기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴실릴기 중에서 선택되는 어느하나이다.The substituent R 2 is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, or a substituted or unsubstituted heteroatom. A heteroaryl group of 2 to 50 carbon atoms having 1 to 3 heteroatoms selected from O, N, S and Si, a substituted or unsubstituted alkoxy group of 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group of 6 to 30 carbon atoms It is any one selected from an aryloxy group, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms.
여기서, 상기 [화합물 a] 내지 [화합물 e]에서의 '치환 또는 비치환된'에서의 '치환'은 중수소, 시아노기, 할로겐기, 히드록시기, 니트로기, 탄소수 1 내지 24의 알킬기, 탄소수 1 내지 24의 할로겐화된 알킬기, 탄소수 2 내지 24의 알케닐기, 탄소수 2 내지 24의 알키닐기, 탄소수 1 내지 24의 헤테로알킬기, 탄소수 6 내지 24의 아릴기, 탄소수 7 내지 24의 아릴알킬기, 탄소수 2 내지 24의 헤테로아릴기 또는 탄소수 2 내지 24의 헤테로아릴알킬기, 탄소수 1 내지 24의 알콕시기, 탄소수 1 내지 24의 알킬아미노기, 탄소수 6 내지 24의 아릴아미노기, 탄소수 1 내지 24의 헤테로 아릴아미노기, 탄소수 1 내지 24의 알킬실릴기, 탄소수 6 내지 24의 아릴실릴기, 탄소수 6 내지 24의 아릴옥시기로 이루어진 군에서 선택된 1개 이상의 치환기로 치환되는 것을 의미한다. Here, 'substitution' in 'substituted or unsubstituted' in [compound a] to [compound e] means deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group with 1 to 24 carbon atoms, and 1 to 2 carbon atoms. Halogenated alkyl group of 24, alkenyl group of 2 to 24 carbon atoms, alkynyl group of 2 to 24 carbon atoms, heteroalkyl group of 1 to 24 carbon atoms, aryl group of 6 to 24 carbon atoms, arylalkyl group of 7 to 24 carbon atoms, 2 to 24 carbon atoms A heteroaryl group or a heteroarylalkyl group having 2 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 6 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, or a heteroarylamino group having 1 to 24 carbon atoms. It means being substituted with one or more substituents selected from the group consisting of an alkylsilyl group having 24 carbon atoms, an arylsilyl group having 6 to 24 carbon atoms, and an aryloxy group having 6 to 24 carbon atoms.
본 발명의 화합물에서 사용되는 치환기인 아릴기는 하나의 수소 제거에 의해서 방향족 탄화수소로부터 유도된 유기 라디칼로, 상기 아릴기가 치환기가 있는 경우 서로 이웃하는 치환기와 서로 융합 (fused)되어 고리를 추가로 형성할 수 있다. The aryl group, which is a substituent used in the compound of the present invention, is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen. When the aryl group has a substituent, it can be fused with neighboring substituents to further form a ring. You can.
상기 아릴기의 구체적인 예로는 페닐기, o-비페닐기, m-비페닐기, p-비페닐기, o-터페닐기, m-터페닐기, p-터페닐기, 나프틸기, 안트릴기, 페난트릴기, 피레닐기, 인데닐, 플루오레닐기, 테트라히드로나프틸기, 페릴렌일, 크라이세닐, 나프타세닐, 플루오란텐일 등과 같은 방향족 그룹을 들 수 있고, 상기 아릴기 중 하나 이상의 수소 원자는 중수소 원자, 할로겐 원자, 히드록시기, 니트로기, 시아노기, 실릴기, 아미노기 (-NH2, -NH(R), -N(R')(R''), R'과 R"은 서로 독립적으로 탄소수 1 내지 10의 알킬기이며, 이 경우 "알킬아미노기"라 함), 아미디노기, 히드라진기, 히드라존기, 카르복실기, 술폰산기, 인산기, 탄소수 1 내지 24의 알킬기, 탄소수 1 내지 24의 할로겐화된 알킬기, 탄소수 1 내지 24의 알케닐기, 탄소수 1 내지 24의 알키닐기, 탄소수 1 내지 24의 헤테로알킬기, 탄소수 6 내지 24의 아릴기, 탄소수 6 내지 24의 아릴알킬기, 탄소수 2 내지 24의 헤테로아릴기 또는 탄소수 2 내지 24의 헤테로아릴알킬기로 치환될 수 있다. Specific examples of the aryl group include phenyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, naphthyl group, anthryl group, phenanthryl group, Aromatic groups such as pyrenyl group, indenyl, fluorenyl group, tetrahydronaphthyl group, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc. are included, and at least one hydrogen atom of the aryl group is a deuterium atom or a halogen atom. , hydroxy group, nitro group, cyano group, silyl group, amino group (-NH 2 , -NH(R), -N(R')(R''), R' and R" are independently of one another and have 1 to 10 carbon atoms. an alkyl group, in this case referred to as an “alkylamino group”), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, alkyl group with 1 to 24 carbon atoms, halogenated alkyl group with 1 to 24 carbon atoms, 1 to 24 carbon atoms alkenyl group, alkynyl group having 1 to 24 carbon atoms, heteroalkyl group having 1 to 24 carbon atoms, aryl group having 6 to 24 carbon atoms, arylalkyl group having 6 to 24 carbon atoms, heteroaryl group having 2 to 24 carbon atoms, or It may be substituted with a heteroarylalkyl group.
본 발명의 화합물에서 사용되는 치환기인 헤테로아릴기는 N, O, P, Si, S, Ge, Se, Te 중에서 선택된 1, 2 또는 3개의 헤테로원자를 포함하고, 나머지 고리 원자가 탄소인 탄소수 2 내지 24의 고리 방향족 시스템을 의미하며, 상기 고리들은 융합(fused)되어 고리를 형성할 수 있다. 그리고 상기 헤테로아릴기 중 하나 이상의 수소 원자는 상기 아릴기의 경우와 마찬가지의 치환기로 치환가능하다.The heteroaryl group, which is a substituent used in the compound of the present invention, contains 1, 2, or 3 heteroatoms selected from N, O, P, Si, S, Ge, Se, and Te, and has 2 to 24 carbon atoms, with the remaining ring atoms being carbon. refers to a ring aromatic system, and the rings can be fused to form a ring. And one or more hydrogen atoms of the heteroaryl group may be replaced with the same substituent as that of the aryl group.
또한 본 발명에서 상기 방향족 헤테로고리는 방향족 탄화수소 고리에서 방향족 탄소중 하나이상이 N, O, P, Si, S, Ge, Se, Te 중에서 선택된 하나 이상의 헤테로 원자로 치환된 것을 의미하며, 바람직하게는 1 내지 4개의 헤테로 원자로 치환된 것일 수 있다. In addition, in the present invention, the aromatic heterocycle means that one or more aromatic carbons in an aromatic hydrocarbon ring are substituted with one or more heteroatoms selected from N, O, P, Si, S, Ge, Se, and Te, preferably 1. It may be substituted with up to 4 heteroatoms.
본 발명에서 사용되는 치환기인 알킬기의 구체적인 예로는 메틸, 에틸, 프로필, 이소프로필, 이소부틸, sec-부틸, tert-부틸, 펜틸, iso-아밀, 헥실 등을 들 수 있고, 상기 알킬기 중 하나 이상의 수소 원자는 원자는 상기 아릴기의 경우와 마찬가지의 치환기로 치환가능하다.Specific examples of the alkyl group as a substituent used in the present invention include methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, etc., and one or more of the alkyl groups The hydrogen atom can be substituted with the same substituent as in the case of the aryl group.
본 발명의 화합물에서 사용되는 치환기인 알콕시기의 구체적인 예로는 메톡시, 에톡시, 프로폭시, 이소부틸옥시, sec-부틸옥시, 펜틸옥시, iso-아밀옥시, 헥실옥시 등을 들 수 있고, 상기 알콕시기 중 하나 이상의 수소 원자는 상기 아릴기의 경우와 마찬가지의 치환기로 치환가능하다.Specific examples of the alkoxy group as a substituent used in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, etc., One or more hydrogen atoms of the alkoxy group may be replaced with the same substituent as that of the aryl group.
본 발명의 화합물에서 사용되는 치환기인 실릴기의 구체적인 예로는 트리메틸실릴, 트리에틸실릴, 트리페닐실릴, 트리메톡시실릴, 디메톡시페닐실릴, 디페닐메틸실릴, 디페닐비닐실릴, 메틸사이클로뷰틸실릴, 디메틸퓨릴실릴 등을 들 수 있고, 상기 실릴기 중 하나 이상의 수소 원자는 상기 아릴기의 경우와 마찬가지의 치환기로 치환가능 하다.Specific examples of the silyl group as a substituent used in the compound of the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, and methylcyclobutylsilyl. , dimethylfurylsilyl, etc., and one or more hydrogen atoms of the silyl group may be replaced with the same substituent as that of the aryl group.
이하, 본 발명에 따른 피리딘 그룹을 포함하는 방향족 화합물을 제조하는 방법을 보다 상세하게는 설명하도록 한다.Hereinafter, the method for producing an aromatic compound containing a pyridine group according to the present invention will be described in more detail.
본 발명의 첫 번째 단계인 a) 단계는, [반응식 1]내, 화합물 a로 표시되는 피리딘 유도체의 산화 반응으로부터 화합물 b로 표시되는 화합물을 제조하는 단계이며, 이에 관해 하기에서 설명하도록 한다.Step a), the first step of the present invention, is a step of preparing a compound represented by compound b from the oxidation reaction of a pyridine derivative represented by compound a in [Scheme 1], which will be described below.
<피리딘 유도체의 산화 반응><Oxidation reaction of pyridine derivative>
상기 단계 a)는 하기 [반응식 1]내, 화합물 a로 표시되는 피리딘 유도체의 산화 반응으로부터 화합물 b로 표시되는 피리딘-N-옥사이드 유도체를 합성하는 단계이다.Step a) is a step of synthesizing a pyridine-N-oxide derivative represented by compound b from the oxidation reaction of a pyridine derivative represented by compound a in the following [Scheme 1].
[반응식 1][Scheme 1]
상기 a)단계에서의 화합물 a로 표시되는 피리딘 유도체의 산화 반응은 산화제로 피리딘 또는 피리딘 유도체를 산화시킬 수 있는 산화제는 어떠한 것도 사용할 수 있으며, 산소, 과산화수소(H2O2), 산소, 과산화수소(H2O2), 메타클로로퍼벤조익에시드(m-chloro perbenzoic acid,mCPBA), 디메틸디옥시렌(Dimethyldioxirane) 중에서 선택되는 어느 하나 또는 이들의 혼합물을 이용할 수 있다.In the oxidation reaction of the pyridine derivative represented by compound a in step a), any oxidizing agent capable of oxidizing pyridine or a pyridine derivative can be used, including oxygen, hydrogen peroxide (H 2 O 2 ), oxygen, hydrogen peroxide ( H 2 O 2 ), m -chloro perbenzoic acid (mCPBA), dimethyldioxirane, or a mixture thereof may be used.
이때, 산화제의 사용량은 상기 피리딘 또는 피리딘 유도체 1 몰 당량에 대하여 1 내지 5몰 당량으로 사용하는 것이 바람직하다. 산화제의 사용량이 1몰 당량보다 작을 경우에는 원하는 전환율을 얻을 수 없으며, 5몰 당량을 초과하여 사용하여도 더 이상 전환율이 증가하지 않으므로 더 이상 사용할 필요는 없다.At this time, the oxidizing agent is preferably used in an amount of 1 to 5 mole equivalents per 1 mole equivalent of the pyridine or pyridine derivative. If the amount of oxidizing agent used is less than 1 molar equivalent, the desired conversion rate cannot be obtained, and even if it is used in excess of 5 molar equivalents, the conversion rate does not increase any further, so there is no need to use it any more.
상기 피리딘 유도체의 산화 반응에서 과산화수소를 산화제로 사용할 경우 유기 촉매를 사용할 수 있으며, 아세트산(acetic acid)을 단독으로 촉매로 사용하거나 아세트산과 황산을 함께 촉매로 사용하는 방법이 있다. 다른 방법으로는 말레인산(maleic acid) 또는 무수말레인산(maleic acid anhydride), 프탈산(phthalic acid) 또는 무수프탈산(phthalic acid anhydride)과 같은 카르복실산 유도체를 촉매로 사용하는 방법이 있으나, 이에 제한되는 것은 아니다.When hydrogen peroxide is used as an oxidizing agent in the oxidation reaction of the pyridine derivative, an organic catalyst can be used. There is a method of using acetic acid alone as a catalyst or acetic acid and sulfuric acid together as catalysts. Other methods include, but are limited to, using maleic acid or carboxylic acid derivatives such as maleic acid anhydride, phthalic acid, or phthalic acid anhydride as catalysts. no.
a) 단계에서의 산화 반응의 반응조건은 30~150 ℃ 온도 범위인 것이 바람직하며, 산화 반응을 30℃ 미만의 온도에서 실시하는 경우에는 반응 진행이 매우 느리며, 150℃를 초과하는 온도에서 실시할 경우에는 산화제, 예를 들면 과산화수소의 증발과 분해를 촉진시켜 산화제, 예를 들면 과산화수소의 반응의 참여가 거의 이루어지지 않는다.The reaction conditions for the oxidation reaction in step a) are preferably in the temperature range of 30 to 150 ℃. If the oxidation reaction is carried out at a temperature below 30 ℃, the reaction progresses very slowly, and if carried out at a temperature exceeding 150 ℃. In this case, evaporation and decomposition of the oxidizing agent, such as hydrogen peroxide, are promoted, so that the oxidizing agent, such as hydrogen peroxide, hardly participates in the reaction.
또한 상기 산화 반응은 1~30 시간 동안 실시하는 것이 바람직하며, 1시간 미만으로 실시하는 경우에는 전환율이 매우 낮고, 30시간을 초과하여 실시하여도 더 이상의 전환율 증가는 나타나지 않으므로 30시간을 초과하여 실시할 필요는 없다.In addition, the oxidation reaction is preferably carried out for 1 to 30 hours. When carried out for less than 1 hour, the conversion rate is very low, and even if carried out for more than 30 hours, no further increase in conversion rate is observed, so it is carried out for more than 30 hours. You don't have to.
상기 단계 b)는 하기 [반응식 2]내, 화합물 b로 표시되는 피리딘-N-옥사이드 유도체 내 치환기 -R1-H의 할로겐화 반응으로부터 화합물 c로 표시되는 화합물을 합성하는 단계이며, 이에 관해 하기에서 설명하도록 한다.Step b) is a step of synthesizing the compound represented by compound c from the halogenation reaction of the substituent -R1-H in the pyridine-N-oxide derivative represented by compound b in the following [Scheme 2], which is explained below. Let's do it.
[반응식 2] [Scheme 2]
본 발명에 있어서 할로겐화 반응은, 화합물 일부가 할로겐 원소로 치환되는 반응로서, 염소화 반응(chlorination reaction), 불소화 반응(fluorination reaction), 브롬화 반응(bromination reaction) 등을 포함하는 것이며, 바람직하게는 염소화 반응일 수 있다.In the present invention, the halogenation reaction is a reaction in which part of a compound is replaced with a halogen element, and includes chlorination reaction, fluorination reaction, bromination reaction, etc., preferably chlorination reaction. It can be.
상기 b)단계에서의 할로겐화 반응은 치환기 -R1-H의 말단 탄소를 PCl3, PBr3, POCl3 , 트리클로로이소시아누릭산(trichloroisocyanuric acid), HBr, Bromosucciniminde, I2, Iodosuccinimide, Trifluoromethanesulfonimide 중에서 선택되는 어느 하나 또는 이들의 혼합물로 수행할 수 있다.The halogenation reaction in step b) is performed by replacing the terminal carbon of the substituent -R1-H with PCl3, PBr3, POCl 3 , trichloroisocyanuric acid, HBr, Bromosucciniminde, I 2 , Iodosuccinimide, Trifluoromethanesulfonimide. It can be performed with any one selected from among them or a mixture thereof.
또한 상기 할로겐화 반응은, 예를 들면, 테트라에틸암모늄 클로라이드, 트리에틸아민, 또는 디메틸아닐린 또는 디에틸아닐린의 존재 또는 부재하에, 그리고 클로로포름, 1,2-디클로로에탄, 디클로로메탄, 톨루엔, 자일렌, 또는 아세토니트릴과 같은 추가적 용매의 존재 또는 부재하에 상승된 온도(예를 들어 60 내지 120℃)에서 화합물 b로 표시되는 화합물을 PCl3, PBr3, POCl3 ~ 또는 이들의 혼합물, 또는 POBr3와 반응시켜 제조될 수 있다.The halogenation reaction can also be carried out, for example, in the presence or absence of tetraethylammonium chloride, triethylamine, or dimethylaniline or diethylaniline, and in the presence or absence of chloroform, 1,2-dichloroethane, dichloromethane, toluene, xylene, or prepared by reacting the compound represented by compound b with PCl3, PBr3, POCl 3 or mixtures thereof, or POBr3 at elevated temperature (e.g. 60 to 120° C.) in the presence or absence of an additional solvent such as acetonitrile. It can be.
상기 단계 c)는 하기 [반응식 3]내, 화합물 c로 표시되는 화합물과 화합물 d로 표시되는 화합물의 알킬화 반응으로부터 화합물 e로 표시되는 피리딘 그룹을 포함하는 방향족 화합물을 합성하는 단계이며, 이에 관해 하기에서 설명하도록 한다.Step c) is a step of synthesizing an aromatic compound containing a pyridine group, represented by compound e, from the alkylation reaction of the compound represented by compound c and the compound represented by compound d in the following [Scheme 3]. This will be explained later.
[반응식 3][Scheme 3]
상기 c)단계에서 알킬화 반응은 프리델 크라프트(Friedel-Craft) 반응인 것이 바람직하며, 프리델 크라프트(Friedel-Craft) 반응은 루이스 산 촉매 하에서 친전자성 방향족 치환반응을 통하여 알킬화된 생성물을 수득할 수 있는 반응이다. In step c), the alkylation reaction is preferably a Friedel-Craft reaction, and the Friedel-Craft reaction is an alkylated product that can be obtained through an electrophilic aromatic substitution reaction under a Lewis acid catalyst. It's a reaction.
구체적으로, 화합물 d로 표시되는 화합물을 c로 표시되는 화합물과 루이스 산(Lewis acid)의 존재 하에서 반응시켜서 상기 화합물 d로 표시되는 화합물의 방향족 고리에 알킬화(alkylation)가 일어나도록 하는 반응을 의미하는 것으로서, 상기 반응을 통하여 벤젠 고리와 같은 방향족 고리에 새로운 탄소-탄소 결합이 형성되게 된다. Specifically, it refers to a reaction in which the compound represented by compound d is reacted with the compound represented by c in the presence of a Lewis acid to cause alkylation to occur in the aromatic ring of the compound represented by compound d. As a result, through the above reaction, a new carbon-carbon bond is formed in an aromatic ring such as a benzene ring.
상기 프리델-크래프츠 알킬화 반응에 있어서 적당한 것으로 알려진 루이스 산 촉매들은 AlCl3, FeCl3및 TiCl4를 포함하나, 이에 제한되는 것은 아니다.Lewis acid catalysts known to be suitable for the Friedel-Crafts alkylation reaction include, but are not limited to, AlCl 3 , FeCl 3 and TiCl 4 .
촉매의 선택은 특정한 생성물이 선택적으로 형성되는 지의 여부에(하나보다 더 많은 생성물의 가능성이 존재하는 경우)에 영향을 미치고 따라서 촉매는 반응으로부터 기대되는 생성물 또는 생성물들에 따라 촉매가 선택될 수 있다. 적합하게 둘 또는 그이상의 적당한 촉매들을 조합(combination)하는 것이 이용될 수 있을 것으로 생각된다. 그러나, 단일 촉매의 사용이 바람직하다. 택일적으로 또는 부가적으로 선택성은 온도, 압력, 유량(연속 공정인 경우) 및 반응물들의 농도 중에 어느 하나 또는 그 이상을 독립적으로 변화시켜 조절될 수 있다.The choice of catalyst affects whether a particular product is selectively formed (if more than one product possibility exists) and thus a catalyst may be selected depending on the product or products expected from the reaction. . It is believed that a combination of two or more suitable catalysts may be used. However, the use of a single catalyst is preferred. Alternatively or additionally, selectivity can be adjusted by independently varying one or more of temperature, pressure, flow rate (if a continuous process), and concentration of reactants.
상기 c)단계에서 알킬화 반응의 반응조건은 반응이 대기압에서 수행되는 경우 30~150 ℃의 온도조건에서, 1~30 시간의 반응시간인 것이 바람직하다.The reaction conditions for the alkylation reaction in step c) are preferably 1 to 30 hours at a temperature of 30 to 150°C when the reaction is performed at atmospheric pressure.
본 발명에 따라 제조되는 피리딘 그룹을 포함하는 방향족 화합물은 상기 반응식 3 내 화합물 e로 표시되는 화합물로서, 분자 구조 내 피리딘기와 방향족 고리를 동시에 포함하고 있다.The aromatic compound containing a pyridine group prepared according to the present invention is a compound represented by compound e in Scheme 3, and contains both a pyridine group and an aromatic ring in its molecular structure.
이때, 방향족 고리내 질소(N) 원자가 치환된 경우 화합물의 탈수소화 엔탈피를 감소시킴으로써 열역학적으로 수소의 방출을 유리하게 하며, 또한 방향족 고리내 치환기의 도입도 화합물의 탈수소화 엔탈피를 감소시키는 요인으로 작용할 수 있다.At this time, when the nitrogen (N) atom in the aromatic ring is substituted, it thermodynamically favors the release of hydrogen by reducing the dehydrogenation enthalpy of the compound, and the introduction of a substituent in the aromatic ring also acts as a factor in reducing the dehydrogenation enthalpy of the compound. You can.
이하 본 발명에 따른 피리딘 그룹을 포함하는 방향족 화합물을 수소 저장 물질로 사용하기 위한 평가 결과를 도 1 내지 도 5에 도시하였다. Hereinafter, the evaluation results for using the aromatic compound containing a pyridine group according to the present invention as a hydrogen storage material are shown in Figures 1 to 5.
도 1은 디시클로헥실메탄(dicyclohexylmethane)에 대한 N-치환 및 메틸기(CH3) 첨가 효과에 따른 계산된 탈수소화 엔탈피 값과 이론 수소 저장 용량을 나타내며, 2번의 화합물과 같이 화합물 내 메틸기의 도입이 없을 경우 탈수소화 반응시 질소(N) 원자를 포함하는 방향족 고리의 열림 반응이 진행될 염려가 있으며, 4번 또는 6번의 화합물과 같이 N-치환의 방향족 고리만으로 이루어진 화합물의 수소화 및 탈수소화 진행이 어려운 문제점이 존재한다.Figure 1 shows the calculated dehydrogenation enthalpy value and theoretical hydrogen storage capacity according to the effect of N-substitution and methyl group (CH 3 ) addition to dicyclohexylmethane, and like compound 2, the introduction of a methyl group in the compound If it is not present, there is a risk that the opening reaction of the aromatic ring containing the nitrogen (N) atom will proceed during the dehydrogenation reaction, and it is difficult to proceed with hydrogenation and dehydrogenation of compounds consisting of only N-substituted aromatic rings, such as compounds no. 4 or 6. There is a problem.
방향족 고리내 치환기의 도입의 구체적인 예로서, 상기 [반응식 3]에서 상기 화합물 e 내 치환기 R2는 치환 또는 비치환된 탄소수 1 내지 30의 알킬기인 것이 화합물의 탈수소화 엔탈피를 감소시키는 측면에서 바람직하며, 더욱 바람직하게는 상기 치환기 R2는 메틸기인 것이 수소 저장 밀도 (H2 storage density)를 높이는 측면에서 바람직하다.As a specific example of introduction of a substituent in an aromatic ring, in [Scheme 3], the substituent R 2 in the compound e is preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms in terms of reducing the enthalpy of dehydrogenation of the compound. , more preferably, the substituent R 2 is a methyl group in terms of increasing hydrogen storage density (H 2 storage density).
상기 [반응식 1] 내지 [반응식 3]에서 상기 치환기 R1는 메틸렌기인 것이 수소 저장 밀도 (H2 storage density)를 높이는 측면에서 바람직하다. In [Reaction Scheme 1] to [Reaction Scheme 3], it is preferable that the substituent R 1 is a methylene group in terms of increasing hydrogen storage density (H 2 storage density).
본 발명에 따라 제조된 피리딘 그룹을 포함하는 방향족 화합물은 반응기에서 금속 함유 촉매와 접촉하고 공정에서 수소를 결합 또는 방출하는 것을 특징으로 하고, 여기서, 수소 로딩 및 수소 언로딩을 위해 사용된 금속 함유 촉매는, 다공성 무극성 운반체 상에서 미세하게 분할된 형태의 금속인 팔라듐, 니켈, 백금, 이리듐, 루테늄, 코발트, 로듐, 구리, 금, 레늄, 및 철 중 하나 이상을 포함할 수 있으나, 다공성 무극성 운반체 상에서 팔라듐을 포함하는 것이 금속 함유 촉매의 단가를 절약하는 측면에서 바람직하다.The aromatic compound comprising a pyridine group prepared according to the invention is characterized in that it contacts a metal-containing catalyst in the reactor and binds or releases hydrogen in the process, wherein the metal-containing catalyst used for hydrogen loading and hydrogen unloading may include one or more of palladium, nickel, platinum, iridium, ruthenium, cobalt, rhodium, copper, gold, rhenium, and iron, which are metals in finely divided form on a porous non-polar carrier, but palladium on a porous non-polar carrier It is preferable in terms of saving the unit cost of the metal-containing catalyst.
또한, 본 명세서에 기재된 실시예와 도면에 도시된 구성은 본 발명의 가장 바람직한 일 실시예에 불과할 뿐이고 본 발명의 기술적 사상을 모두 대변하는 것은 아니므로, 본 출원시점에 있어서 이들을 대체할 수 있는 다양한 균등물과 변형 예들이 있을 수 있음을 이해하여야 한다.In addition, the embodiments described in this specification and the configurations shown in the drawings are only one of the most preferred embodiments of the present invention and do not represent the entire technical idea of the present invention, so at the time of filing the present application, various methods that can replace them are available. It should be understood that equivalents and variations may exist.
이하, 첨부된 도면을 참조하여 본 발명에 따른 피리딘 유도체를 포함하는 방향족 화합물을 제조하는 방법 및 수소화, 탈수소화 반응에 대한 실시예 및 비교예 등을 통하여 상세히 설명한다.Hereinafter, with reference to the attached drawings, a method for producing an aromatic compound containing a pyridine derivative according to the present invention and hydrogenation and dehydrogenation reactions will be described in detail through examples and comparative examples.
합성예 1: 2-(n-methylbenzyl)pyridine isomers (MBP)의 합성Synthesis Example 1: Synthesis of 2-(n-methylbenzyl)pyridine isomers (MBP)
하기에 도시된 2-(n-methylbenzyl)pyridine isomers (MBP)의 합성방법은 본 발명에 따른 수소 저장 물질로 사용이 가능한 피리딘 그룹을 포함하는 방향족 화합물을 제조하는 방법의 대표적인 예를 나타낸다.The method for synthesizing 2-(n-methylbenzyl)pyridine isomers (MBP) shown below represents a representative example of a method for producing an aromatic compound containing a pyridine group that can be used as a hydrogen storage material according to the present invention.
<2-(n-methylbenzyl)pyridine isomers (MBP)의 합성방법><Synthesis method of 2-(n-methylbenzyl)pyridine isomers (MBP)>
합성예 1-1: 2-methylpyridine n-oxide의 합성Synthesis Example 1-1: Synthesis of 2-methylpyridine n-oxide
2-picoline (Alfa Aesar) 306 mmol과 H2O2 (Samchun Chemicals) 626 mmol를 아세트산(acetic acid) 120 mL에 주입하여 혼합물 용액을 제조한 후, 혼합물 용액을 80 ㅀC 온도에서 24 시간동안 교반시켜준다. 혼합물 용액을 감압 조건에서 증류시켜 혼합물 용액 내 아세트산(acetic acid)과 미반응 반응물을 제거시켜 연노란색의 고체 화합물인 2-methylpyridine n-oxide(30.94 g, 92.6 %)를 수득한다.A mixture solution was prepared by injecting 306 mmol of 2-picoline (Alfa Aesar) and 626 mmol of H 2 O 2 (Samchun Chemicals) into 120 mL of acetic acid, and then the mixture solution was stirred at 80 ㅀC for 24 hours. Let me do it. The mixture solution was distilled under reduced pressure to remove acetic acid and unreacted reactants in the mixture solution to obtain 2-methylpyridine n-oxide (30.94 g, 92.6 %), a light yellow solid compound.
1H-NMR (400 MHz, CDCl3): δ = 8.28 (d, 1H, J = 6.8 Hz), 7.30 (dd, 1H, J = 2.0, 7.5 Hz), 7.20 (m, 2H), 2.54 (s, 1H). 13C NMR (100 MHz, CDCl3): δ = 17.75, 123.55, 125.54, 126.51, 139.32, 149.00.1H-NMR (400 MHz, CDCl 3 ): δ = 8.28 (d, 1H, J = 6.8 Hz), 7.30 (dd, 1H, J = 2.0, 7.5 Hz), 7.20 (m, 2H), 2.54 (s, 1H). 13C NMR (100 MHz, CDCl3): δ = 17.75, 123.55, 125.54, 126.51, 139.32, 149.00.
합성예 1-2: 2-(chloromethyl)pyridine의 합성Synthesis Example 1-2: Synthesis of 2-(chloromethyl)pyridine
아르곤 분위기 하에서 디클로로메탄(dichloromethane) 15.18 mL에 POCl3 (Sigma-Aldrich) 159 mmol이 용해된 POCl3 용액을 디클로로메탄(dichloromethane) 34 mL에 2-methylpyridine n-oxide 122 mmol이 용해된 2-methylpyridine n-oxide 용액에 적가시켜 준다. POCl3 용액의 1/10 가량이 적가되었을 때, 디클로로메탄(dichloromethane) 7.84 mL에 트리에틸아민(triethylamine)이 용해된 트리에틸아민 용액을 POCl3 용액의 주입속도와 동일하게 2-methylpyridine n-oxide 용액에 적가시켜준다. POCl3 용액을 모두 적가시켜 준 후, 반응물 용액을 3 시간동안 환류시켜 반응을 진행한 뒤, 반응물 용액 내 얼음을 첨가하여 반응을 종료시키고, 탄산수소나트륨(NaHCO3)을 첨가하여 반응물 용액을 중성상태로 전환시킨다. 반응물 용액 내 디클로로메탄(dichloromethane)과 소금물(brine)을 추가적으로 첨가하여 유기층으로 합성물을 추출한다. 합성물이 분산된 유기 용액에 황산마그네슘(MgSO4)을 첨가하여 수분을 제거시킨 후, 진공 상태에서 농축하여 2-(chloromethyl)pyridine (10.408 g, 80.6 %)를 수득하였다.Under an argon atmosphere, a POCl 3 solution containing 159 mmol of POCl 3 (Sigma-Aldrich) dissolved in 15.18 mL of dichloromethane was mixed with 2-methylpyridine n, in which 122 mmol of 2-methylpyridine n-oxide was dissolved in 34 mL of dichloromethane. -Add it dropwise to the oxide solution. When about 1/10 of the POCl 3 solution was added dropwise, the triethylamine solution containing triethylamine dissolved in 7.84 mL of dichloromethane was injected with 2-methylpyridine n-oxide at the same injection rate as the POCl 3 solution. Add it dropwise to the solution. After adding all of the POCl 3 solution dropwise, the reaction solution was refluxed for 3 hours to proceed with the reaction. Ice was added to the reaction solution to terminate the reaction, and sodium bicarbonate (NaHCO 3 ) was added to neutralize the reaction solution. Convert to state. The composite is extracted into the organic layer by additionally adding dichloromethane and brine to the reactant solution. Magnesium sulfate (MgSO4) was added to the organic solution in which the composite was dispersed to remove moisture, and then concentrated in vacuum to obtain 2-(chloromethyl)pyridine (10.408 g, 80.6 %).
합성예 1-3: 2-(n-methylbenzyl)pyridine isomers (MBP)의 합성Synthesis Example 1-3: Synthesis of 2-(n-methylbenzyl)pyridine isomers (MBP)
2-(chloromethyl)pyridine 200 mmol를 0 ℃에서 톨루엔(toluene) 1.4 mol(7 eq.; Samchun Chemicals)에 aluminum chloride anhydride 320 mmol(1.6 eq.; Alfa-Aesar)이 용해된 용액에 적가시켜 2-(chloromethyl)pyridine를 용해시킨 후, 90 ℃에서 16 시간동안 반응시킨다. 반응물 용액 내 얼음을 첨가하여 반응을 종료시키고, 수산화나트륨(NaOH)을 첨가하여 반응물 용액을 중성상태로 전환시킨다. 반응물 용액 내 에틸아세테이트(ethyl acetate)과 소금물(brine)을 추가적으로 첨가하여 유기층으로 합성물을 추출한다. 합성물이 분산된 유기 용액에 황산마그네슘(MgSO4)을 첨가하여 수분을 제거시킨 후, 진공 상태에서 농축한다. 농축된 합성물을 103 ℃, 0.1 torr 조건에서 갑압증류하여 최종 생성물인 2-(n-methylbenzyl)pyridine isomers (MBP) (32.99 g, 90%)를 수득하였다.200 mmol of 2-(chloromethyl)pyridine was added dropwise to a solution of 320 mmol (1.6 eq.; Alfa-Aesar) of aluminum chloride anhydride in 1.4 mol of toluene (7 eq.; Samchun Chemicals) at 0°C. After dissolving (chloromethyl)pyridine, react at 90°C for 16 hours. The reaction is terminated by adding ice to the reactant solution, and the reactant solution is converted to a neutral state by adding sodium hydroxide (NaOH). The composite is extracted into the organic layer by additionally adding ethyl acetate and brine to the reactant solution. Magnesium sulfate (MgSO 4 ) is added to the organic solution in which the composite is dispersed to remove moisture, and then concentrated under vacuum. The concentrated composite was distilled under reduced pressure at 103°C and 0.1 torr to obtain the final product, 2-(n-methylbenzyl)pyridine isomers (MBP) (32.99 g, 90%).
1H NMR (300 MHz, CDCl3): δ = 2.25, 2.31 (s, 3H), 4.12, 4.19 (s, 2H), 7.07-.17 (m, 6H), 7.72 (d, J = 1.8, 7.7 Hz, 1H), 8.58 (t, J = 4.3 Hz, 1H). 1H NMR (300 MHz, CDCl3): δ = 2.25, 2.31 (s, 3H), 4.12, 4.19 (s, 2H), 7.07-.17 (m, 6H), 7.72 (d, J = 1.8, 7.7 Hz, 1H), 8.58 (t, J = 4.3 Hz, 1H).
13C NMR (100 MHz, CDCl3): δ = 19.74, 21.03, 21.39, 42.30, 44.13, 44.52, 121.17, 121.26, 122.79, 123.16, 123.23, 126.17, 126.84, 127.20, 128.50, 129.01, 129.31, 129.91, 130.22, 130.43, 135.96, 136.29, 136.67, 136.77, 136.86, 138.22, 149.02, 149.07, 160.62, 161.17. 13C NMR (100 MHz, CDCl3): δ = 19.74, 21.03, 21.39, 42.30, 44.13, 44.52, 121.17, 121.26, 122.79, 123.16, 123.23, 126.17, 126.84, 127. 20, 128.50, 129.01, 129.31, 129.91, 130.22, 130.43 , 135.96, 136.29, 136.67, 136.77, 136.86, 138.22, 149.02, 149.07, 160.62, 161.17.
HR-MS (m/z): [M+H+] calcd. for [C13H14N], 184.1048; anal.184.1124.HR-MS (m/z): [M+H+] calcd. for [C13H14N], 184.1048; anal.184.1124.
1) 화학적 분석1) Chemical analysis
1H 및 13C NMR 스펙트럼은 Bruker DPX-300 FT-NMR 분광계로 각각 300MHz 및 400MHz 주파수에서 측정된다. 질량스펙트럼 데이터는 한국 기초 과학 연구소의 SYNAPT G2 고해상도질량 분석기로 분석하였다. 비등점은 질소(N2) 분위기 하에서 연속 가열 속도 10 Kmin-1에서 DSC Q1000를 이용하여 측정 하였다 1 H and 13 C NMR spectra are measured at frequencies of 300 MHz and 400 MHz, respectively, with a Bruker DPX-300 FT-NMR spectrometer. Mass spectral data were analyzed with a SYNAPT G2 high-resolution mass spectrometer at the Korea Basic Science Research Institute. The boiling point was measured using DSC Q1000 at a continuous heating rate of 10 Kmin -1 under a nitrogen (N 2 ) atmosphere.
융점은 한국 기초 과학 연구소의 DSC 8000를 사용하여 질소(N2) 분위기 하에서 5 Kmin-1의 연속 가열 속도로 -80℃ ~ 50℃ 또는 -60℃ ~ 50℃에서 측정하였다.The melting point was measured at -80°C to 50°C or -60°C to 50°C at a continuous heating rate of 5 Kmin -1 under a nitrogen (N 2 ) atmosphere using DSC 8000 of the Korea Basic Science Research Institute.
2) 수소화 반응(Hydrogenation Reaction)2) Hydrogenation Reaction
유리 라이너 (100 cm3)를 갖는 고압 Parr 반응기에서, 반응물(15 cm3)에 시판되거나 합성된 Ru/Al2O3가 적재되었으며, 여기서 금속 촉매(M)와 반응물(R)의 비율(M/R)은 0.05 내지 0.30 몰%의 범위이다. 반응기 내부를 질소(N2) 기체로 퍼징시킨 후, 반응기를 수소 가스(H2, 99.9 %) 50 bar로 가압하여 배압 조절기를 사용하여 반응 동안 유지시켰다. 반응기 내 온도가 150 ℃에 접근하면, 교반 속도 1200rpm에서 수소화 반응을 소정 시간 진행하였다. 교반 및 가열을 중단 한 후, 반응기를 실온으로 냉각시켰다. 전체 수소화 생성물에 대한 선택성 및 수소 저장 효율은 하기 표 1에 기재 하였다.In a high-pressure Parr reactor with a glass liner (100 cm 3 ), the reactants (15 cm 3 ) were loaded with commercially available or synthesized Ru/Al 2 O 3 , where the ratio of metal catalyst (M) to reactant (R) (M /R) ranges from 0.05 to 0.30 mol%. After purging the inside of the reactor with nitrogen (N 2 ) gas, the reactor was pressurized to 50 bar of hydrogen gas (H 2 , 99.9%) and maintained during the reaction using a back pressure regulator. When the temperature in the reactor approached 150°C, the hydrogenation reaction was performed for a predetermined time at a stirring speed of 1200 rpm. After stopping stirring and heating, the reactor was cooled to room temperature. The selectivity and hydrogen storage efficiency for the total hydrogenation product are listed in Table 1 below.
(℃, bar)temperature, pressure
(℃, bar)
(mol%, wt%)M/R
(mol%, wt%)
(hour)hour
(hour)
(mol%)conversion rate
(mol%)
(mol%)selectivity
(mol%)
(%)H 2 storage efficiency
(%)
Al2O3 5 wt% Ru/
Al 2 O 3
0.030.05,
0.03
Al2O3 5 wt% Ru/
Al 2 O 3
0.050.08,
0.05
Al2O3 5 wt% Ru/
Al 2 O 3
0.050.08,
0.05
Al2O3 5 wt% Ru/
Al 2 O 3
0.130.23,
0.13
0.130.23,
0.13
0.130.23,
0.13
0.130.23,
0.13
0.170.30,
0.17
3) 탈수소화 반응(Dehydrogenation Reaction)3) Dehydrogenation Reaction
Pt 및 Pd 지지 촉매는 탈수소화 반응은 회분식 유리 반응기 (90 cm3)를 사용하였으며. 탄소 혹은 알루미나에 지지된 Pt 혹은 Pd 촉매를 반응 전에 반응 용기의 바닥에 미리 장입한 후, 반응물(7.732 mmol)을 반응기 내에 주입하였다. 여기서 금속 촉매(M)와 반응물(R)의 비율(M/R)은 0.1 내지 0.6 몰% 범위이다. 내부의 수분 및 산소를 제거하기 위해 10분 동안 질소(N2) 가스를 퍼징 한 후, 반응기를 230 ℃에서 19 분간, 250 ℃에서 22 분간 또는 270 ℃에서 25 분간 열전 사식 순환 재킷을 사용하여 가열하였다. 탈수소화 반응이 4 시간 동안 수행되는 동안, 방출된 수소(H2) 가스의 부피는 유리 뷰렛에서 옮겨진 물의 양으로 측정되었다. 교반은 수소 생성 속도에 영향을 미치지 않았으며, 반응이 완료되면 반응기를 실온으로 냉각시켰다. GC 결과로부터 산출된 수소(H2) 가스의 몰수는 뷰렛에 의해 측정된 수소(H2) 가스의 몰과 유사하였다. 탈수소화 생성물에 대한 선택성 및 수소 생성 수율은 하기 표 2 및 도 2에 기재하였다.A batch glass reactor (90 cm 3 ) was used for the dehydrogenation reaction of the Pt and Pd supported catalysts. A Pt or Pd catalyst supported on carbon or alumina was previously charged to the bottom of the reaction vessel before reaction, and then the reactant (7.732 mmol) was injected into the reactor. Here, the ratio (M/R) of the metal catalyst (M) and the reactant (R) is in the range of 0.1 to 0.6 mol%. After purging with nitrogen (N 2 ) gas for 10 min to remove moisture and oxygen inside, the reactor was heated using a thermal circulation jacket at 230 °C for 19 min, 250 °C for 22 min, or 270 °C for 25 min. did. While the dehydrogenation reaction was carried out for 4 hours, the volume of hydrogen (H 2 ) gas released was measured as the amount of water transferred in a glass burette. Agitation did not affect the rate of hydrogen production, and the reactor was cooled to room temperature once the reaction was complete. The number of moles of hydrogen (H 2 ) gas calculated from the GC results was similar to the moles of hydrogen (H 2 ) gas measured by a burette. Selectivity for dehydrogenation products and hydrogen production yields are shown in Table 2 and Figure 2 below.
(℃)temperature
(℃)
(mol%, wt%)M/R
(mol%, wt%)
(mol%)conversion rate
(mol%)
(mol%)selectivity
(mol%)
(mol%)H 2 yield
(mol%)
(cm3)H 2 production volume
( cm3 )
(1 wt%)PT/C
(1 wt%)
0.1000.1,
0.100
(56.7)643.1
(56.7)
(1 wt%)Pt/Al 2 O 3
(1 wt%)
0.1000.1,
0.100
(53.4)605.6
(53.4)
(1 wt%)PD/C
(1 wt%)
0.0540.1,
0.054
(99.9)1132.4
(99.9)
(1 wt%)Pd/Al 2 O 3
(1 wt%)
0.0540.1,
0.054
(92.2)1045.7
(92.2)
(1 wt%)PD/C
(1 wt%)
0.0540.1,
0.054
(58.4)662.3
(58.4)
(1 wt%)PD/C
(1 wt%)
0.0540.1,
0.054
(30.2)342.5
(30.2)
(1 wt%)PD/C
(1 wt%)
0.1090.2,
0.109
(95.4)1082.0
(95.4)
(1 wt%)PD/C
(1 wt%)
0.2170.4,
0.217
(72.7)824.5
(72.7)
(1 wt%)PD/C
(1 wt%)
0.3260.6,
0.326
(85.4)968.6
(85.4)
(1 wt%)PT/C
(1 wt%)
0.1000.1,
0.100
(99.9)1132.4
(99.9)
(1 wt%)Pt/Al 2 O 3
(1 wt%)
0.1000.1,
0.100
(95.2)1079.7
(95.2)
(1 wt%)PD/C
(1 wt%)
0.0540.1,
0.054
(57.0)646.5
(57.0)
(1 wt%)Pd/Al 2 O 3
(1 wt%)
0.0540.1,
0.054
(47.9)543.3
(47.9)
(1 wt%)PT/C
(1 wt%)
0.1000.1,
0.100
(56.6)641.9
(56.6)
(1 wt%)PT/C
(1 wt%)
0.1000.1,
0.100
(26.4)299.4
(26.4)
(1 wt%)PT/C
(1 wt%)
0.2000.2,
0.200
(97.2)1102.4
(97.2)
(1 wt%)PT/C
(1 wt%)
0.4000.4,
0.400
(45.4)514.9
(45.4)
(1 wt%)PT/C
(1 wt%)
0.6000.6,
0.600
(72.5)822.3
(72.5)
도 2는 Pd/C 촉매를 사용하여 H12-MBP과 Pt/C 촉매를 사용하여 H12-BT을 a) 230, 250 및 270 ℃ 각각의 온도에서 M/R = 1 mol% 일 때 탈수소화 반응시 산소 발생을 시간에 따라 도시한 그래프이며, b) 230 ℃에서 M/R = 4 mol%일 때와 M/R = 6 mol %일 때의 탈수소화 반응시 산소 발생을 시간에 따라 도시한 그래프이다.Figure 2 shows a) dehydrogenation of H 12 -MBP using a Pd/C catalyst and H 12 -BT using a Pt/C catalyst when M/R = 1 mol% at each temperature of 230, 250, and 270 °C. This is a graph showing oxygen generation over time during the reaction. b) It is a graph showing oxygen generation over time during the dehydrogenation reaction at 230°C when M/R = 4 mol% and M/R = 6 mol%. It's a graph.
여기서, 반응 시간에 따른 수소 발생 몰%를 도시한 도 2-a)를 보면, 반응기내 온도가 올라갈수록 수소 발생 수율이 증가하는 것을 확인하였으며, 반응 시간에 따른 수소 발생를 비교하여 보면, Pd/C 촉매를 사용하여 H12-MBP로부터 수소를 생성시킨 경우가 Pt/C 촉매를 사용하여 H12-BT로부터 수소를 발생시킨 경우보다 수소 발생 속도가 빠른 것을 확인 하였다. Here, looking at Figure 2-a), which shows the mole % of hydrogen generation according to reaction time, it was confirmed that the hydrogen generation yield increases as the temperature in the reactor increases. Comparing the hydrogen generation according to reaction time, Pd/C It was confirmed that when hydrogen was generated from H 12 -MBP using a catalyst, the hydrogen generation rate was faster than when hydrogen was generated from H 12 -BT using a Pt/C catalyst.
또한 도 2-b)에서 확인한 바와 같이, 금속 촉매(M)와 반응물(R)의 비율(M/R)이 높을수록 탈수소화 반응시 수소 발생 속도가 더욱 증가하는 것을 확인하였다.Additionally, as confirmed in Figure 2-b), it was confirmed that the higher the ratio (M/R) of the metal catalyst (M) and the reactant (R), the more the hydrogen generation rate increases during the dehydrogenation reaction.
이상으로 본 발명은 첨부된 도면 및 실시예를 참조하여 설명되었으나, 이는 예시적인 것에 불과하며, 당해 기술에 속하는 분야에서 통상의 지식을 가진 자라면 이로부터 다양한 변형 및 균등한 타 실시예가 가능하다는 것을 이해할 것이다. 따라서 본 발명의 기술적 보호범위는 아래의 청구범위에 의해서 정하여져야 할 것이다. The present invention has been described above with reference to the accompanying drawings and examples, but these are merely illustrative, and those skilled in the art will recognize that various modifications and other equivalent embodiments are possible therefrom. You will understand. Therefore, the scope of technical protection of the present invention should be determined by the claims below.
Claims (9)
b) 하기 [반응식 2]내, 화합물 b로 표시되는 화합물내 치환기 -R1-H의 할로겐화 반응으로부터 화합물 c로 표시되는 화합물을 제조하는 단계; 및
c) 하기 [반응식 3]내, 화합물 c로 표시되는 화합물과 화합물 d로 표시되는 화합물의 알킬화 반응으로부터 화합물 e로 표시되는 화합물을 제조하는 단계;를 포함하는, 피리딘 그룹을 포함하는 방향족 화합물을 제조하는 방법.
[반응식 1]
[반응식 2]
[반응식 3]
상기 [반응식 1] 내지 [반응식 3]에서,
상기 X는 Cl, Br, I 로부터 선택되는 어느 하나의 할로겐이며,
상기 치환기 R1는 메틸렌, 에틸렌, 프로필렌, 이소프로필렌, 이소부틸렌, sec-부틸렌, tert-부틸렌, 펜틸렌, iso-아밀렌, 헥실렌 중에서 선택되는 알킬렌기이며,
상기 치환기 R2는 비치환된 탄소수 1 내지 30의 알킬기이고,
상기 a)단계에서의 화합물 a로 표시되는 피리딘 유도체의 산화 반응은 산소, 과산화수소(H2O2), 메타클로로퍼벤조익에시드(m-chloro perbenzoic acid,mCPBA), 디메틸디옥시렌(Dimethyldioxirane) 중에서 선택되는 어느 하나 또는 이들의 혼합물을 이용하여 이루어지며;
상기 b)단계에서의 할로겐화 반응은 치환기 -R1-H의 말단 수소를 PCl3, PBr3, POCl3, SOCl2, 트리클로로이소시아누릭산(trichloroisocyanuric acid), HBr, Bromosucciniminde, I2, Iodosuccinimide, Trifluoromethanesulfonimide 중에서 선택되는 어느 하나 또는 이들의 혼합물을 사용하여 할로겐화함으로써, 이루어지고;
상기 c)단계에서 알킬화 반응은 프리델 크라프트(Friedel-Craft) 반응이다.a) Preparing a compound represented by compound b from the oxidation reaction of a pyridine derivative represented by compound a in the following [Scheme 1];
b) preparing a compound represented by compound c from the halogenation reaction of the substituent -R1-H in the compound represented by compound b in the following [Scheme 2]; and
c) preparing a compound represented by compound e from an alkylation reaction of a compound represented by compound c and a compound represented by compound d in the following [Scheme 3]; Preparing an aromatic compound containing a pyridine group, including: How to.
[Scheme 1]
[Scheme 2]
[Scheme 3]
In [Reaction Scheme 1] to [Reaction Scheme 3],
X is any halogen selected from Cl, Br, and I,
The substituent R 1 is an alkylene group selected from methylene, ethylene, propylene, isopropylene, isobutylene, sec-butylene, tert-butylene, pentylene, iso-amylene, and hexylene,
The substituent R 2 is an unsubstituted alkyl group having 1 to 30 carbon atoms,
The oxidation reaction of the pyridine derivative represented by compound a in step a) is oxygen, hydrogen peroxide (H 2 O 2 ), m -chloro perbenzoic acid (mCPBA), and dimethyldioxirane. It is made using any one selected from or a mixture thereof;
The halogenation reaction in step b) is performed by changing the terminal hydrogen of the substituent -R1-H to PCl 3 , PBr 3 , POCl 3 , SOCl 2 , trichloroisocyanuric acid, HBr, Bromosucciniminde, I 2 , Iodosuccinimide, Trifluoromethanesulfonimide. It is achieved by halogenation using any one selected from or a mixture thereof;
The alkylation reaction in step c) is a Friedel-Craft reaction.
상기 [반응식 1] 내지 [반응식 3]에서 상기 치환기 R1는 메틸렌기인 것을 특징으로 하는 피리딘 그룹을 포함하는 방향족 화합물을 제조하는 방법.According to paragraph 1,
A method for producing an aromatic compound containing a pyridine group, wherein in [Scheme 1] to [Scheme 3], the substituent R 1 is a methylene group.
상기 [반응식 3]에서 상기 치환기 R2는 메틸기인 것을 특징으로 하는 피리딘 그룹을 포함하는 방향족 화합물을 제조하는 방법.According to paragraph 1,
In [Scheme 3], the substituent R 2 is a methyl group. A method for producing an aromatic compound containing a pyridine group.
상기 a)단계에서의 산화 반응의 반응조건은 30~150 ℃, 1~30 시간의 반응시간을 가지는 것을 특징으로 하는 피리딘 그룹을 포함하는 방향족 화합물을 제조하는 방법.According to paragraph 1,
The reaction conditions for the oxidation reaction in step a) are 30 to 150° C. and a reaction time of 1 to 30 hours. A method for producing an aromatic compound containing a pyridine group.
상기 단계 c)에서 알킬화 반응의 반응조건은 30~150 ℃이며, 1~30 시간의 반응시간을 가지는 것을 특징으로 하는 피리딘 그룹을 포함하는 방향족 화합물을 제조하는 방법.According to paragraph 1,
A method for producing an aromatic compound containing a pyridine group, wherein the reaction conditions for the alkylation reaction in step c) are 30 to 150° C. and the reaction time is 1 to 30 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020190001272A KR102622005B1 (en) | 2019-01-04 | 2019-01-04 | The Method of Producing Aromatic Compound Comprising Pyridin Group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020190001272A KR102622005B1 (en) | 2019-01-04 | 2019-01-04 | The Method of Producing Aromatic Compound Comprising Pyridin Group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20200085132A KR20200085132A (en) | 2020-07-14 |
| KR102622005B1 true KR102622005B1 (en) | 2024-01-10 |
Family
ID=71526882
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020190001272A KR102622005B1 (en) | 2019-01-04 | 2019-01-04 | The Method of Producing Aromatic Compound Comprising Pyridin Group |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR102622005B1 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104974077A (en) | 2015-06-25 | 2015-10-14 | 黄荣辉 | Synthetic method of 2-chloromethylpyridinehydrochloride |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5431647B2 (en) * | 2003-05-06 | 2014-03-05 | エアー．プロダクツ．アンド．ケミカルス．インコーポレーテッド | Hydrogen storage by reversible hydrogenation of pi-conjugated substrates |
| DE102012221809A1 (en) * | 2012-11-28 | 2014-05-28 | Bayerische Motoren Werke Aktiengesellschaft | Liquid compounds and processes for their use as hydrogen storage |
| KR101862012B1 (en) * | 2016-09-09 | 2018-05-30 | 한국화학연구원 | System for storage and release of hydrogen using pyridine-based hydrogen storage materials |
| KR101845515B1 (en) | 2016-09-30 | 2018-04-04 | 한국과학기술연구원 | Liquid hydrogen storage material and methods of storaging hydrogen using the same |
-
2019
- 2019-01-04 KR KR1020190001272A patent/KR102622005B1/en active IP Right Grant
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104974077A (en) | 2015-06-25 | 2015-10-14 | 黄荣辉 | Synthetic method of 2-chloromethylpyridinehydrochloride |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20200085132A (en) | 2020-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hohloch et al. | Copper (I) complexes of normal and abnormal carbenes and their use as catalysts for the Huisgen [3+ 2] cycloaddition between azides and alkynes | |
| Boubakri et al. | Synthesis and catalytic applications of palladium N-heterocyclic carbene complexes as efficient pre-catalysts for Suzuki–Miyaura and Sonogashira coupling reactions | |
| KR101350206B1 (en) | Ruthenium-catalyzed cycloaddition of alkynes and organic azides | |
| Barz et al. | Transition metal complexes with organoazide ligands: synthesis, structural chemistry, and reactivity | |
| KR102586087B1 (en) | Processes for the preparation of a diarylthiohydantoin compound | |
| PL203798B1 (en) | Catalysts for hydrosilylation reactions | |
| KR102658286B1 (en) | Buchwald-Hartwig arylation method for the preparation of tertiary aryl amines | |
| Yadav et al. | Direct construction of 2-alkylbenzo-1, 3-azoles via C–H activation of alkanes for C–C and C–X (X= O, S) bond formation | |
| EP1944308B1 (en) | Process for production of ortho-metallized 1:3 complex of iridium with homoligand | |
| KR20210094035A (en) | A raw material for chemical vapor deposition containing a ruthenium complex and a chemical vapor deposition method using the raw material for chemical vapor deposition | |
| CN111253305B (en) | Alkenyl or alkylation reaction method of alkyl substituted azaarene | |
| KR102622005B1 (en) | The Method of Producing Aromatic Compound Comprising Pyridin Group | |
| Singewald et al. | Novel RhI Piano‐Stool Complexes with New Hemilabile Ligands Ligating through Phosphane and Arene Groups: Synthesis, Characterization, and Reactivity | |
| CN109734703B (en) | Preparation method of indoline-7-carboxylic ester compound | |
| Seneclauze et al. | Design and preparation of neutral substituted fluorene-and carbazole-based platinum (II)–acetylide complexes | |
| Qian et al. | ONO pincer palladium (II) complexes featuring furoylhydrazone ligands: Synthesis, characterization and catalytic activity towards Suzuki–Miyaura coupling reaction | |
| CN111875637B (en) | Phosphine ligand and synthesis method and application thereof | |
| Cheng et al. | Synthesis and catalytic activity of pyrazolyl-functionalized N-heterocyclic carbene palladium complexes | |
| Sheokand et al. | 1, 2, 3-Triazolyl bisphosphine with pyridyl functionality: synthesis, copper (i) chemistry and application in click catalysis | |
| Matos et al. | Palladium complexes based on tridentate pyrazolyl-ligands: Synthesis, structures and use in Suzuki cross-coupling reactions | |
| CN105658627A (en) | Monoarylation of aromatic amines | |
| Yafele et al. | New symmetrical N^ N^ N palladium (II) pincer complexes: synthesis, characterization and catalytic evaluation in the Suzuki-Miyaura cross-coupling reaction | |
| JPS62292756A (en) | Manufacture of 2,2,6,6-tetraalkylpiperidine derivative | |
| CN110229133B (en) | Synthetic method of flavonoid compound | |
| Van Wyk et al. | Solvent-free synthesis of 3, 5-di-tert-butylpyrazole and 3, 5-di-substituted-butylpyrazol-1-ylethanol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right |