CN107253920B - A kind of fragrance azobenzene oxide compound and preparation method thereof - Google Patents
A kind of fragrance azobenzene oxide compound and preparation method thereof Download PDFInfo
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- CN107253920B CN107253920B CN201710563212.4A CN201710563212A CN107253920B CN 107253920 B CN107253920 B CN 107253920B CN 201710563212 A CN201710563212 A CN 201710563212A CN 107253920 B CN107253920 B CN 107253920B
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- yellow solid
- aromatic nitro
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 78
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000003205 fragrance Substances 0.000 title claims description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 27
- -1 aromatic nitro compound Chemical class 0.000 claims abstract description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims description 64
- 239000000758 substrate Substances 0.000 claims description 41
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 38
- 239000003960 organic solvent Substances 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 27
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 23
- 229910017604 nitric acid Inorganic materials 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 18
- 239000012298 atmosphere Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 239000002585 base Substances 0.000 claims description 13
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 150000002736 metal compounds Chemical class 0.000 claims description 10
- 239000010970 precious metal Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 9
- 150000002220 fluorenes Chemical class 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 claims description 6
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 claims description 5
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 claims description 5
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- SNWQUNCRDLUDEX-UHFFFAOYSA-N inden-1-one Chemical compound C1=CC=C2C(=O)C=CC2=C1 SNWQUNCRDLUDEX-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 claims description 3
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical group CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 2
- 239000000975 dye Substances 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- GAUZCKBSTZFWCT-UHFFFAOYSA-N azoxybenzene Chemical compound C=1C=CC=CC=1[N+]([O-])=NC1=CC=CC=C1 GAUZCKBSTZFWCT-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 239000003208 petroleum Substances 0.000 description 15
- 230000005311 nuclear magnetism Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 229940126062 Compound A Drugs 0.000 description 10
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 10
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 9
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229940079593 drug Drugs 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000011097 chromatography purification Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 235000011167 hydrochloric acid Nutrition 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 2
- SODQFLRLAOALCF-UHFFFAOYSA-N 1lambda3-bromacyclohexa-1,3,5-triene Chemical compound Br1=CC=CC=C1 SODQFLRLAOALCF-UHFFFAOYSA-N 0.000 description 2
- PEXGTUZWTLMFID-UHFFFAOYSA-N 2-phenyldiazenylphenol Chemical compound OC1=CC=CC=C1N=NC1=CC=CC=C1 PEXGTUZWTLMFID-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 229940126543 compound 14 Drugs 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000007540 photo-reduction reaction Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 1
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 1
- GMGLGUFSJCMZNT-UHFFFAOYSA-N BrCCCCCC.BrCCCCCC Chemical compound BrCCCCCC.BrCCCCCC GMGLGUFSJCMZNT-UHFFFAOYSA-N 0.000 description 1
- 241000662429 Fenerbahce Species 0.000 description 1
- 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 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- OPPWASLOVKWHCT-UHFFFAOYSA-N boric acid;phenol Chemical compound OB(O)O.OC1=CC=CC=C1 OPPWASLOVKWHCT-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229940125797 compound 12 Drugs 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000006578 reductive coupling reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/10—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/06—Compounds containing nitro groups bound to a carbon skeleton having nitro groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a kind of fragrant azobenzene oxide compounds and preparation method thereof.The present invention uses under alkaline condition for the first time, and Photoinduced Reduction aromatic nitro compound is azoxybenzene.Different aromatic nitro compounds is synthesized first；Secondly under the conditions of potassium hydroxide, toluene and isopropanol, the reduction of nitro is carried out under the irradiation of xenon lamp, synthesizes fragrant azobenzene oxide compound.The preparation method that the present invention develops has many advantages, such as that component is simple, reaction condition is mild, low toxic and environment-friendly and selectivity are high；The azoxy compound obtained accordingly dyestuff, liquid crystal material and in terms of have potential application.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to a kind of fragrance azobenzene oxide compound and preparation method thereof.
Background technique
Fragrant azobenzene oxide compound is not only important functional material, in dyestuff, drug, food additives and liquid
Brilliant material etc. has important application, and is also important organic synthesis intermediate, can further be reduced into fragrant even
Nitrogen compound is oxidized to aromatic amine；Meanwhile it can also be rearranged into hydroxyazobenzene, provide for the synthesis of hydroxyazobenzene
Convenient and fast approach.Since aromatic series azoxy compound and aromatic azo-compound have similar structure so that its
There are many general character with aromatic azo-compound in terms of property and function, therefore to fragrant azobenzene oxide compound property and function
The research of energy will be an important issue.Based on the important application value of fragrant azobenzene oxide compound, synthetic method
Have many reports.
However, more or less all coming with some shortcomings in existing synthetic method.Traditional synthetic method all employs greatly
Toxic substance or reaction condition is harsher.The method of glucose reduction is most classic method, it require that higher
Reaction temperature and stringent feed ratio, and yield is relatively low；And existing catalyst preparation is complicated, and the introducing of metal can make
At environmental pollution.Therefore, it is necessary to develop a kind of method of the fragrant azobenzene oxide compound of preparation efficiently, less toxic, environmentally friendly.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of fragrant azobenzene oxide compound under light illumination will be fragrant
Nitro compound is reduced into fragrant azobenzene oxide compound, and preparation is simple, high income, environmentally protective.
In order to achieve the above objectives, the present general inventive concept is single nitroaromatic, in xenon lamp irradiation, argon atmosphere
Under the conditions of, reductive coupling is carried out to the nitro of each substrate and obtains aromatic series azoxybenzene.
Specific technical solution of the invention is: a kind of fragrance azobenzene oxide compound, chemical structural formula is following
One of structural formula:
The preparation method of above-mentioned fragrance azobenzene oxide compound, mainly comprises the steps that
(1) aromatic nitro substrate is prepared using one of following preparation method；
1. light yellow solid is prepared using concentrated nitric acid, fluorenes as raw material；In the presence of a base, pungent with light yellow solid, 1- bromine
Alkane is that aromatic nitro substrate is prepared in raw material；
2. white solid in the presence of a base, is prepared using carbazole, 1- bromo-dodecane as raw material；Then with concentrated nitric acid, white
Color solid is that aromatic nitro substrate is prepared in raw material；
3. light yellow solid is prepared using concentrated nitric acid, 2- bromine fluorenes as raw material；In the presence of a base, with light yellow solid, 1-
Bromooctane is that aromatic nitro substrate is prepared in raw material；
4. in acetic acid and concentrated hydrochloric acid, faint yellow solid is prepared using indone as raw material；With faint yellow solid, positive fourth
Base lithium, hexyl bromide 1 bromohexane are that yellow solid is prepared in raw material；Aromatic nitro bottom is prepared using yellow solid, concentrated nitric acid as raw material
Object；
5., using paranitroanilinum, connection pinacol borate, nitrite tert-butyl as raw material, being prepared under oxidant
Faint yellow solid；In the presence of carbonate, organic precious metal compounds, with faint yellow solid, 9,9 two octane dibromo fluorenes are raw material
Aromatic nitro substrate is prepared；
6., with 4- hydroxy benzenes pinacol borate, 1,6- dibromo-hexane for raw material, being prepared the in the presence of carbonate
One compound；In the presence of carbonate, organic precious metal compounds, with the first compound, bromo- 9, the 9- dioctyl -9- hydrogen fluorenes of 2-
For raw material, second compound is prepared；In the presence of carbonate, it is prepared into using second compound, 4- nitrophenol as raw material
To aromatic nitro substrate；
(2) after aromatic nitro substrate, toluene, isopropanol, potassium hydroxide being mixed in inert atmosphere, under xenon lamp irradiation,
Reaction obtains fragrant azobenzene oxide compound.
Aromatic nitro substrate of the present invention is compound A, compound B, compound C, compound D, compound E or change
Close object F；
The structural formula of the compound A are as follows:
The structural formula of the compound B are as follows:
The structural formula of the compound C are as follows:
The structural formula of the compound D are as follows:
The structural formula of the compound E are as follows:
The structural formula of the compound F are as follows:
Further preparation method, mainly comprises the steps that
(1) aromatic nitro substrate is prepared using one of following preparation method；
1. fluorenes is added at 0~10 DEG C in mixed organic solvents and concentrated nitric acid, after reacting 15~30min, recrystallization is filtered
After obtain light yellow solid；Then metal base is added in organic solvent, adds light yellow solid；Then it is pungent that 1- bromine is added dropwise
Alkane reacts 25~40min, obtains aromatic nitro substrate；
2. alkali is added in organic solvent under ice-water bath, carbazole is then added；Then 1- bromo-dodecane is added dropwise；Then room temperature
11~15 h of lower reaction, obtain white solid；At 0~10 DEG C white solid is added, instead in mixed organic solvents and concentrated nitric acid
15~30 min are answered, then extracts, be recrystallized to give aromatic nitro substrate；
3. fluorenes is added at 0~10 DEG C in mixed organic solvents and concentrated nitric acid, after reacting 15~30 min, recrystallization is taken out
Light yellow solid is obtained after filter；Then metal base is added in organic solvent, adds light yellow solid；Then it is pungent that 1- bromine is added dropwise
Alkane reacts 10~15 h, obtains aromatic nitro substrate；
4. indone is added in acetic acid and concentrated hydrochloric acid, 15~18 h are reacted at 100 DEG C, obtain faint yellow solid；It takes yellowish
Color solid is added in organic solvent, and under inert atmosphere protection, n-BuLi is added dropwise；Then it is added dropwise bromohexane, following reaction 10~
15 h, obtain yellow solid；Under ice-water bath, extracting yellow solid is added in organic solvent, and concentrated nitric acid, reaction 55~70 is then added dropwise
Min obtains aromatic nitro substrate；
5. organic solvent is added in paranitroanilinum, connection pinacol borate and oxidant under inert atmosphere protection
In, at 20~25 DEG C, nitrite tert-butyl organic solvent solution is added dropwise, reacts 3~5 h, obtains faint yellow solid；Successively will
9,9 two octane dibromo fluorenes, carbonate solution, organic precious metal compounds and organic solvent are added in faint yellow solid, 80
10~15h is reacted at DEG C, obtains aromatic nitro substrate；
6. sequentially adding carbonate, 4- hydroxy benzenes pinacol borate, organic solvent in reactor, at 60 DEG C, it is added
1,6- dibromo-hexane reacts 3~5 h；Obtain the first compound；In inert atmosphere atmosphere, is sequentially added in the reactor
Bromo- 9, the 9- dioctyl -9- hydrogen fluorenes of one compound, 2-, organic precious metal compounds, organic solvent, carbonate, react at 80 DEG C
6~8 h；Obtain second compound；Second compound, carbonate, organic solvent are sequentially added in the reactor, are stirred at 80 DEG C
15~30 min are mixed, 4- nitrophenol is then added dropwise, the reaction was continued 5~7 h obtain aromatic nitro substrate；
(2) alkali, aromatic nitro substrate, toluene, isopropanol, the toluene and isopropanol volume ratio are sequentially added in reactor
For 1:1, aromatic nitro substrate and alkali molar ratio are 1:2；Then in inert atmosphere atmosphere, xenon lamp (power 250-1000
W it under)/sunlight irradiation, is reacted to obtain fragrant azobenzene oxide compound；Reaction time is 8~20 h.
In above-mentioned technical proposal, in step (1) and step (2), purification processes are carried out to product, purification step is, first
(20 mL*3) is extracted with dichloromethane, it is then dry with anhydrous sodium sulfate, it filters, is spin-dried for；After being spin-dried for, column chromatography, expansion are carried out
Agent is methylene chloride and petroleum ether (PE:DCM=20:1-5:1, volume ratio), and component needed for collecting is spin-dried for, and vacuum drying oven is dry
It is dry, obtain product.
In above-mentioned technical proposal, concentrated nitric acid mass concentration is 65%；Alkali is KOH；Organic solvent is dichloroethanes, dimethyl
Sulfoxide, acetone, tetrahydrofuran, acetonitrile, N,N-dimethylformamide；The mass concentration of concentrated hydrochloric acid is 35%；Inert atmosphere is argon gas
Atmosphere；Oxidant is dibenzoyl peroxide；Carbonate is potassium carbonate；Organic precious metal compounds are tetrakis triphenylphosphine palladium.
In above-mentioned technical proposal, reaction system component is few, mild condition, and yield is high, and selectivity is high, without idol in reaction process
Pyridine and aromatic amine generate.
Light has important application as a kind of clean energy resource in organic synthesis field, but all needs in traditional scheme
In conjunction with transition metal or dyestuff, to pollute the environment and the wasting of resources.The present invention directly uses xenon lamp spoke for the first time
Fragrant azobenzene oxide compound is prepared according to aromatic nitro substrate, and does not add any transition metal or dyestuff during the reaction
Equal substances, more environment-friendly high-efficiency.
The invention also discloses above-mentioned aromatic nitro substrates and preparation method thereof, and prepare fragrant oxidation in the presence of a base
Application in azobenzene compound.
Due to the implementation of above scheme, compared with prior art, the present invention having the advantage that
Mild condition, component is simple, and yield is high during 1. the present invention discloses the fragrant azobenzene oxide compound of preparation,
Side reaction is few, and selectivity is high, generates in reaction process without aromatic azo-compound and aromatic amine.
It is and existing 2. synthesize fragrant azobenzene oxide compound using xenon lamp irradiation aromatic nitro substrate in the present invention
Synthetic method is compared, at low cost, easy to operate, does not use metal ion, low toxic and environment-friendly, and the development for being more in line with green industry is wanted
It asks.Simultaneously under the irradiation of sunlight, can also efficiently it react.
Detailed description of the invention
Fig. 1 is the nuclear-magnetism figure of compound A；
Fig. 2 is the nuclear-magnetism figure of compound B；
Fig. 3 is the nuclear-magnetism figure of compound C；
Fig. 4 is the nuclear-magnetism figure of compound D；
Fig. 5 is the nuclear-magnetism figure of compound E；
Fig. 6 is the nuclear-magnetism figure of compound F；
Fig. 7 is the nuclear-magnetism figure of the fragrant azobenzene oxide compound of compound A preparation；
Fig. 8 is the nuclear-magnetism figure of the fragrant azobenzene oxide compound of compound B preparation；
Fig. 9 is the nuclear-magnetism figure of the fragrant azobenzene oxide compound of compound C preparation；
Figure 10 is the nuclear-magnetism figure of the fragrant azobenzene oxide compound of compound D preparation；
Figure 11 is the nuclear-magnetism figure of the fragrant azobenzene oxide compound of compound E preparation；
Figure 12 is the nuclear-magnetism figure of the fragrant azobenzene oxide compound of compound F preparation.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described:
Chemical reagent used in the present embodiment: fluorenes, 99%, Aldrich；2- bromine fluorenes, 99%, Aldrich；Four (triphenylphosphines)
Palladium, 99%, Aldrich；Connection pinacol borate, 99%, Aldrich；Paranitroanilinum, 98%, tci；Where is para hydroxybenzene boric acid frequency
Alcohol ester, 98%, Adamas；Indone, 98%, Aldrich；Hexyl bromide 1 bromohexane, 99%, Chinese Medicine (group) Solution on Chemical Reagents in Shanghai is public
Department；1,6- dibromo-hexane, 98%, China Medicine (Group) Shanghai Chemical Reagent Co.,；Dimethyl sulfoxide, 99%, Chinese Medicine (collection
Group) Solution on Chemical Reagents in Shanghai company；Carbazole, 97%, China Medicine (Group) Shanghai Chemical Reagent Co.,；Anhydrous sodium sulfate, hydroxide
Potassium, isopropanol, toluene, acetonitrile, acetic acid, hydrochloric acid, nitric acid analyze pure, China Medicine (Group) Shanghai Chemical Reagent Co.,；Tetrahydro
Furans (THF), methylene chloride, ethyl alcohol, n-hexane and ethyl acetate analyze pure, Chinasun Specialty Products Co., Ltd.
Test equipment and condition: Nuclear Magnetic Resonance: 300 megahertzs；Determination condition: with CDCl3For solvent, with tetramethylsilane
For internal standard compound, test temperature is room temperature.
The synthesis of one aromatic nitro substrate of embodiment
The synthesis of compound A:
80 mL, 1,2 dichloroethanes is added in 250 mL flasks, 20 mL concentrated nitric acids (65%) are then added, make its dispersion
Uniformly, it is reacted in ice-water bath, is then slowly added to 10 g fluorenes, after reacting 20 min, be poured into 300 mL ice methanol,
Light yellow solid 2 (11 g) is obtained after suction filtration.7.5 g KOH are ground into a powder and are added in 100 mL DMSO, are uniformly dispersed,
It is then slowly added into above-mentioned 6.3 g of light yellow solid, 20 min is stirred, 15 mL1- bromooctanes is then added drop-wise to above-mentioned system
In, 30 min are reacted, it is dry with petroleum ether extraction, it is spin-dried for, obtains crude product, petroleum ether is then used to carry out column as solvent
Chromatography obtains yellow viscous liquid, i.e. compound A (9.0 g).
The synthesis of compound B:
150 mL acetone are added in 250 mL flasks, are added to 5.4 g potassium hydroxide grind into powder under ice-water bath
In flask, 10 min are stirred, then 5g carbazole is added slowly in above-mentioned system, 30 min is stirred, then by 11.2 g
1- bromo-dodecane is added drop-wise in above-mentioned system, after dripping off, is reacted 12 h at room temperature, after reaction, is extracted with dichloromethane, with
It uses petroleum ether to carry out column as solvent afterwards to chromatograph to obtain white solid 4 (7.2 g)；0.4 mL nitric acid (65%) is added to
In 100 mL, 1,2 dichloroethanes, temperature is controlled between 0-10 DEG C, after mixing evenly, the above-mentioned white solid of 2 g is added to
In flask, 20 min of reaction are extracted with dichloromethane after reaction, then obtain yellow solid with ethyl alcohol recrystallization, that is, change
It closes object B (1.8 g).
The synthesis of compound C:
80 mL, 1,2 dichloroethanes is added in 250 mL round-bottomed flasks, 20 mL concentrated nitric acids (65%) are then added, make it
It is uniformly dispersed, is then slowly added to 10 g 2- bromine fluorenes at room temperature, after reacting 20 min, be poured into 300 mL ice methanol,
Light yellow solid 6 (10 g) is obtained after suction filtration.10 g KOH are ground into a powder and are added in 80 mL DMSO, are uniformly dispersed, so
After be slowly added to above-mentioned 5 g of light yellow solid, stir 20 min, 7.3 g 1-1- bromooctanes be then added drop-wise to above-mentioned system
In, 12 h are reacted, are extracted with ethyl acetate, anhydrous sodium sulfate is dry, is spin-dried for, obtains crude product, then use petroleum ether as exhibition
Agent progress column is opened to chromatograph to obtain faint yellow solid, i.e. compound C (7.5 g).
The synthesis of compound D:
6.8 g indones are added in 30 mL acetic acid and 15 mL concentrated hydrochloric acids (35%), 16 h, reaction knot are reacted at 100 DEG C
Shu Hou is poured into ice water, is then filtered, and is washed with massive laundering, then with acetone and methylene chloride, is obtained faint yellow solid
8 (4.5 g)；The above-mentioned faint yellow solid of 3.18 g is taken, is added in 50 mL tetrahydrofurans, under argon gas protection, by the positive fourth of 22 mL
Base lithium is slowly dropped in above-mentioned system, after reacting 30 min, 5 mL bromohexanes is added drop-wise in above-mentioned reaction flask, are then reacted
4 h, are then added dropwise 22 mL n-BuLis again, after 30min, then are added dropwise to 5 mL1- bromohexanes, 12 h of following reaction, reaction knot
Shu Hou is added ammonium chloride solution and reaction is quenched, then uses petroleum ether extraction, and make solvent with petroleum ether and carry out column chromatography,
Obtain yellow solid 9 (6.7 g)；Under ice-water bath, the above-mentioned yellow solid of 1.7 g is taken to be added in 120 mL, 1,2 dichloroethanes,
Then 0.42 mL concentrated nitric acid is added drop-wise in above-mentioned system, after dripping off, 1 h of reaction is poured into ice water after reaction
In, it is then extracted with ethyl acetate, carries out column chromatography (petroleum ether: ethyl acetate=20:1) again later and obtain yellow solid, that is, change
It closes object D (1.4 g).
The synthesis of compound E:
Under protection of argon gas, by 1.38 g paranitroanilinum, 2.54 g connection pinacol borate and 49 mg peroxidating two
Benzoyl is added in 60 mL acetonitriles, controls temperature at 25 DEG C, 1.55 g nitrite tert-butyls are then dissolved in 10 mL second
In nitrile, be added drop-wise in above-mentioned system, 4 h of reaction are spin-dried for after reaction, using petroleum ether: ethyl acetate=20:1 is as exhibition
It opens agent and carries out column chromatography, obtain faint yellow solid 11 (1.4 g)；The above-mentioned faint yellow solid of 1g is taken to be added to 25 mL Schlenk bottles
In, then sequentially add 2.24 g, 9,9 two octane dibromo fluorenes, 6 mL solution of potassium carbonate (2 mol/L), 20 mg, tetra- (triphenyl
Phosphine) palladium and 9 mL tetrahydrofurans then three times with biexhaust pipe freezing-pumping-inflation react 12 h, reaction knot at 80 DEG C
Shu Hou is extracted with dichloromethane, and then makees solvent progress column with pure petroleum ether and chromatographs to obtain yellow solid, i.e. compound E
(1.95 g)。
The synthesis of compound F:
K is sequentially added in 250 mL round-bottomed flasks2CO3(2.76 g, 0.02 mol), compound 12 (4.4 g,
0.02 mol) and DMF (60 mL), 20 min are stirred, then 1,6- dibromo-hexane is added in above-mentioned system at 60 DEG C,
React 4 h.It is extracted with dichloromethane after reaction, organic layer is dry with anhydrous sodium sulfate, is spin-dried for (the expansion of rear pillar Chromatographic purification
Agent: ethyl acetate/petroleum ether=1/50), finally obtain pure product 13 (5.6 g).
In argon atmosphere, compound 13 (1 g, 2.6 mmol) are sequentially added in 50 mL round-bottomed flasks, 2- is bromo-
9,9- dioctyl -9- hydrogen fluorenes (1.35 g, 3.1 mmol), (Ph3)4Pd(0) (10 mg, 0.009 mmol),THF (7 mL)
And 2M K2CO3(4 mL).7 h are then reacted at 80 DEG C.It is extracted with dichloromethane after reaction (30 mL*3), it is organic
Layer is dry with anhydrous sodium sulfate, is spin-dried for, and then uses column Chromatographic purification (solvent: ethyl acetate/petroleum ether=1/50), finally
To pure compound 14 (1.36 g).
4- nitrophenol (0.27 g, 1.97mmol), K are sequentially added in 50 mL round-bottomed flasks2CO3 (0.27 g,
1.97 mmol) and DMF (30 mL), 20 min are stirred at 80 DEG C, then add compound 14 (1 g, 1.64 mmol)
Enter into above-mentioned system, the reaction was continued 6 h after dripping；It is extracted with ethyl acetate after reaction, organic layer anhydrous slufuric acid
Sodium is dry, is spin-dried for, and then uses column Chromatographic purification (solvent: ethyl acetate/petroleum ether=1/10), finally obtains pure chemical combination
Object F (0.9 g).
Attached drawing 1-6 is respectively the nuclear-magnetism spectrum of compound A, compound B, compound C, compound D, compound E, compound F
Figure.The yield of obtained correspondence product is respectively as follows: 70%, 82%, 84%, 78%, 95%, 80%.
The above-mentioned process for preparing aromatic nitro substrate is schematically as follows:
The preparation of the fragrant azobenzene oxide compound of embodiment two
Sequentially added in 10 mL ampoule bottles 11.2 mg potassium hydroxide, 0.1 mmol aromatic nitro substrate (compound A,
Compound B, compound C, compound D, compound E or compound F), 3 mL toluene and 3 mL isopropanols, after adding, lead to
10 min deoxygenation of argon gas and tube sealing then react 10 h under xenon lamp (power is that 250-1000 W is optional) irradiation, and reaction terminates
Afterwards, it is extracted with dichloromethane, anhydrous sodium sulfate is dry, is spin-dried for, and then carries out column Chromatographic purification (solvent: petroleum ether/dichloromethane
Alkane), obtain corresponding fragrant azobenzene oxide compound.
Attached drawing 7-12 be respectively compound A, compound B, compound C, compound D, compound E, compound F preparation virtue
The nuclear magnetic spectrogram of fragrant azobenzene oxide compound, the yield of obtained correspondence product are respectively as follows: 97%, 85%, 90%, 91%, 81%,
30%.It is generally acknowledged that conjugacy has crucial effect to photo-reduction, non-conjugated compound is difficult that photoreduction occurs, of the invention
Method is directed to the compound being hardly conjugated, and can still obtain 30% yield, overcome prior art prejudice.
The preparation of the fragrant azobenzene oxide compound of embodiment three (under sunlight illumination)
Sequentially added in 10 mL ampoule bottles 11.2 mg potassium hydroxide, 0.1 mmol compound A, 3 mL toluene and
3 mL isopropanols after adding, lead to 10 min deoxygenation of argon gas and tube sealing, 20 h are then reacted at room temperature under sunlight；Reaction terminates
Afterwards, it is extracted with dichloromethane, anhydrous sodium sulfate is dry, is spin-dried for, and then carries out column Chromatographic purification (solvent: petroleum ether/dichloromethane
Alkane=20/1-8/1), obtain corresponding fragrant azobenzene oxide compound, yield are as follows: 93%.
The above-mentioned process for preparing aromatic nitro substrate is schematically as follows:
。
Claims (6)
1. a kind of preparation method of fragrance azobenzene oxide compound, which comprises the following steps:
(1) aromatic nitro substrate is prepared using one of following preparation method；
1. light yellow solid is prepared using concentrated nitric acid, fluorenes as raw material；In the presence of a base, it is with light yellow solid, 1- bromooctane
Aromatic nitro substrate is prepared in raw material；
2. white solid in the presence of a base, is prepared using carbazole, 1- bromo-dodecane as raw material；Then solid with concentrated nitric acid, white
Body is that aromatic nitro substrate is prepared in raw material；
3. light yellow solid is prepared using concentrated nitric acid, 2- bromine fluorenes as raw material；In the presence of a base, pungent with light yellow solid, 1- bromine
Alkane is that aromatic nitro substrate is prepared in raw material；
4. in acetic acid and concentrated hydrochloric acid, faint yellow solid is prepared using indone as raw material；With faint yellow solid, n-BuLi,
Bromohexane is that yellow solid is prepared in raw material；Aromatic nitro substrate is prepared using yellow solid, concentrated nitric acid as raw material；
5., using paranitroanilinum, connection pinacol borate, nitrite tert-butyl as raw material, being prepared yellowish under oxidant
Color solid；In the presence of carbonate, organic precious metal compounds, with faint yellow solid, 9,9 two octane dibromo fluorenes are raw material preparation
Obtain aromatic nitro substrate；
6., with 4- hydroxy benzenes pinacol borate, 1,6- dibromo-hexane for raw material, the first change is prepared in the presence of carbonate
Close object；It is original with the first compound, bromo- 9, the 9- dioctyl -9- hydrogen fluorenes of 2- in the presence of carbonate, organic precious metal compounds
Material, is prepared second compound；In the presence of carbonate, virtue is prepared using second compound, 4- nitrophenol as raw material
Fragrant nitro substrate；
(2) after mixing aromatic nitro substrate, toluene, isopropanol, alkali in inert atmosphere, under light irradiation, reaction obtains fragrance
Azobenzene oxide compound；
The chemical structural formula of the fragrance azobenzene oxide compound is one of following structural formula:
。
2. the preparation method of fragrant azobenzene oxide compound according to claim 1, which is characterized in that step (1) be with
One of lower preparation method:
1. fluorenes is added at 0~10 DEG C in mixed organic solvents and concentrated nitric acid, after reacting 15~30 min, after recrystallization, suction filtration
Obtain light yellow solid；Then metal base is added in organic solvent, adds light yellow solid；Then 1- bromooctane is added dropwise,
25~40 min are reacted, aromatic nitro substrate is obtained；
2. alkali is added in organic solvent under ice-water bath, carbazole is then added；Then 1- bromo-dodecane is added dropwise；Then anti-at room temperature
11~15 h are answered, white solid is obtained；White solid, reaction 15 is added at 0~10 DEG C in mixed organic solvents and concentrated nitric acid
Then~30 min are extracted, are recrystallized to give aromatic nitro substrate；
3. fluorenes is added at 0~10 DEG C in mixed organic solvents and concentrated nitric acid, after reacting 15~30 min, after recrystallization, suction filtration
Obtain light yellow solid；Then metal base is added in organic solvent, adds light yellow solid；Then 1- bromooctane is added dropwise,
10~15 h are reacted, aromatic nitro substrate is obtained；
4. indone is added in acetic acid and concentrated hydrochloric acid, 15~18 h are reacted at 100 DEG C, obtain faint yellow solid；Take pale yellow colored solid
Body is added in organic solvent, and under inert atmosphere protection, n-BuLi is added dropwise；Then it is added dropwise bromohexane, 10~15 h of following reaction,
Obtain yellow solid；Under ice-water bath, extracting yellow solid is added in organic solvent, and concentrated nitric acid is then added dropwise, and reacts 55~70 min,
Obtain aromatic nitro substrate；
5. paranitroanilinum, connection pinacol borate and oxidant are added in organic solvent under inert atmosphere protection, in
At 20~25 DEG C, nitrite tert-butyl organic solvent solution is added dropwise, reacts 3~5 h, obtains faint yellow solid；Successively by 9,9 2
Octane dibromo fluorenes, carbonate solution, organic precious metal compounds and organic solvent are added in faint yellow solid, anti-at 80 DEG C
10~15 h are answered, aromatic nitro substrate is obtained；
6. sequentially adding carbonate, 4- hydroxy benzenes pinacol borate, organic solvent in reactor, at 60 DEG C, it is added 1,6-
Dibromo-hexane reacts 3~5 h；Obtain the first compound；In inert atmosphere atmosphere, the first change is sequentially added in the reactor
Object, bromo- 9, the 9- dioctyl -9- hydrogen fluorenes of 2-, organic precious metal compounds, organic solvent, carbonate are closed, 6~8 are reacted at 80 DEG C
h；Obtain second compound；Second compound, carbonate, organic solvent are sequentially added in the reactor, stir 15 at 80 DEG C
~30 min, are then added dropwise 4- nitrophenol, and the reaction was continued 5~7 h obtain aromatic nitro substrate.
3. the preparation method of fragrant azobenzene oxide compound according to claim 2, which is characterized in that the concentrated nitric acid matter
Measuring concentration is 65%；Alkali is KOH；Organic solvent is dichloroethanes, dimethyl sulfoxide, acetone, tetrahydrofuran, acetonitrile or N, N-
Dimethylformamide；The mass concentration of concentrated hydrochloric acid is 35%；Inert atmosphere is argon atmosphere；Oxidant is dibenzoyl peroxide；
Carbonate is potassium carbonate；Organic precious metal compounds are tetrakis triphenylphosphine palladium.
4. the preparation method of fragrant azobenzene oxide compound according to claim 1, which is characterized in that step (2) is, instead
It answers and sequentially adds alkali, aromatic nitro substrate, toluene, isopropanol in device, then in inert atmosphere atmosphere, under light irradiation, carry out
Reaction obtains fragrant azobenzene oxide compound.
5. the preparation method of fragrant azobenzene oxide compound according to claim 4, which is characterized in that the toluene and different
The volume ratio of propyl alcohol is 1:1, and the molar ratio of aromatic nitro substrate and alkali is 1:2；The time of reaction is 8~20 h；Light irradiates
Xenon lamp irradiation or sunlight irradiation；Alkali is KOH；Inert atmosphere is argon atmosphere.
6. the preparation method of fragrant azobenzene oxide compound according to claim 1, which is characterized in that in step (1) and
In step (2), purification processes are carried out to product, purification step is first to be extracted with dichloromethane, then dry with anhydrous sodium sulfate
It is dry, it filters, is spin-dried for；After being spin-dried for, column chromatography is carried out, component needed for collecting is spin-dried for, and vacuum drying oven is dry, obtains product.
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