CN114560771B - 一种光催化选择性硝化溴代苯酚的方法 - Google Patents
一种光催化选择性硝化溴代苯酚的方法 Download PDFInfo
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- CN114560771B CN114560771B CN202210218046.5A CN202210218046A CN114560771B CN 114560771 B CN114560771 B CN 114560771B CN 202210218046 A CN202210218046 A CN 202210218046A CN 114560771 B CN114560771 B CN 114560771B
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- Prior art keywords
- guanidine
- silver
- dibromophenol
- bromophenol
- nitrite
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- 238000006396 nitration reaction Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 26
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims abstract description 11
- FNAKEOXYWBWIRT-UHFFFAOYSA-N 2,3-dibromophenol Chemical compound OC1=CC=CC(Br)=C1Br FNAKEOXYWBWIRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000001546 nitrifying effect Effects 0.000 claims abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 5
- DPPGFDBIEYDQOT-UHFFFAOYSA-N [Ag].NC(=N)N Chemical compound [Ag].NC(=N)N DPPGFDBIEYDQOT-UHFFFAOYSA-N 0.000 claims description 26
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- 229910052724 xenon Inorganic materials 0.000 claims description 15
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 13
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- 238000004811 liquid chromatography Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 8
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- AUORDBJGOHYGKR-UHFFFAOYSA-N 3-bromo-2-nitrophenol Chemical compound OC1=CC=CC(Br)=C1[N+]([O-])=O AUORDBJGOHYGKR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- FAXWFCTVSHEODL-UHFFFAOYSA-N 2,4-dibromophenol Chemical compound OC1=CC=C(Br)C=C1Br FAXWFCTVSHEODL-UHFFFAOYSA-N 0.000 claims description 6
- SSIZLKDLDKIHEV-UHFFFAOYSA-N 2,6-dibromophenol Chemical compound OC1=C(Br)C=CC=C1Br SSIZLKDLDKIHEV-UHFFFAOYSA-N 0.000 claims description 6
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 235000010288 sodium nitrite Nutrition 0.000 claims description 6
- PZFMWYNHJFZBPO-UHFFFAOYSA-N 3,5-dibromophenol Chemical compound OC1=CC(Br)=CC(Br)=C1 PZFMWYNHJFZBPO-UHFFFAOYSA-N 0.000 claims description 5
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 239000004304 potassium nitrite Substances 0.000 claims description 5
- 235000010289 potassium nitrite Nutrition 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000010606 normalization Methods 0.000 claims description 2
- 238000000825 ultraviolet detection Methods 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 229910052709 silver Inorganic materials 0.000 abstract description 4
- 239000004332 silver Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 abstract description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- 125000001246 bromo group Chemical group Br* 0.000 abstract 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical class N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 125000002795 guanidino group Chemical group C(N)(=N)N* 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 7
- DCIPFSYBGTWYCR-UHFFFAOYSA-N 5847-59-6 Chemical compound OC1=CC=C([N+]([O-])=O)C=C1Br DCIPFSYBGTWYCR-UHFFFAOYSA-N 0.000 description 6
- VEJSIOPQKQXJAT-UHFFFAOYSA-N 2-bromo-6-nitrophenol Chemical compound OC1=C(Br)C=CC=C1[N+]([O-])=O VEJSIOPQKQXJAT-UHFFFAOYSA-N 0.000 description 5
- CUTFAPGINUFNQM-UHFFFAOYSA-N 4-bromo-2-nitrophenol Chemical compound OC1=CC=C(Br)C=C1[N+]([O-])=O CUTFAPGINUFNQM-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- VJQGLUHOAIZTNK-UHFFFAOYSA-N 3-bromo-5-nitrophenol Chemical compound OC1=CC(Br)=CC([N+]([O-])=O)=C1 VJQGLUHOAIZTNK-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 238000002474 experimental method Methods 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 230000000802 nitrating effect Effects 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000002051 biphasic effect Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- JKDQJTZCMWRKJA-UHFFFAOYSA-N 1-bromo-3-nitro-5-phenylmethoxybenzene Chemical compound [O-][N+](=O)C1=CC(Br)=CC(OCC=2C=CC=CC=2)=C1 JKDQJTZCMWRKJA-UHFFFAOYSA-N 0.000 description 1
- INIXUZNHFXUIMA-UHFFFAOYSA-N 2,4-dibromo-6-nitrophenol Chemical compound OC1=C(Br)C=C(Br)C=C1[N+]([O-])=O INIXUZNHFXUIMA-UHFFFAOYSA-N 0.000 description 1
- CDVNZMKTJIBBBV-UHFFFAOYSA-N 2-methyl-3,5-dinitrobenzoic acid Chemical compound CC1=C(C(O)=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O CDVNZMKTJIBBBV-UHFFFAOYSA-N 0.000 description 1
- SZYVPWPBRABKAB-UHFFFAOYSA-N 3-bromo-4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C(Br)=C1 SZYVPWPBRABKAB-UHFFFAOYSA-N 0.000 description 1
- MNOJRWOWILAHAV-UHFFFAOYSA-N 3-bromophenol Chemical compound OC1=CC=CC(Br)=C1 MNOJRWOWILAHAV-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- FIJXQBUMQGSMKD-UHFFFAOYSA-N 5-bromo-2-(methoxymethoxy)pyridine Chemical compound COCOC1=CC=C(Br)C=N1 FIJXQBUMQGSMKD-UHFFFAOYSA-N 0.000 description 1
- DTWHNSNSUBKGTC-UHFFFAOYSA-N 5-bromo-2-nitrophenol Chemical compound OC1=CC(Br)=CC=C1[N+]([O-])=O DTWHNSNSUBKGTC-UHFFFAOYSA-N 0.000 description 1
- 101710112752 Cytotoxin Proteins 0.000 description 1
- 241001522296 Erithacus rubecula Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229940122344 Peptidase inhibitor Drugs 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 102000005763 Thrombopoietin Receptors Human genes 0.000 description 1
- 108010070774 Thrombopoietin Receptors Proteins 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000000641 acridinyl group Chemical class C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- -1 aryl phenols Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000005130 benzoxazines Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 231100000599 cytotoxic agent Toxicity 0.000 description 1
- 239000002619 cytotoxin Substances 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 229960001069 eltrombopag Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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Abstract
本发明为一种光催化选择性硝化溴代苯酚的方法，涉及光催化有机合成和精细化工领域。具体以可见光为能源，亚硝酸盐为硝化试剂，银掺杂胍基修饰氮化碳为催化剂，在乙腈和水的溶剂中，选择性硝化二溴代苯酚制得兼有溴代和硝基官能团的苯酚中间体。与传统硝化工艺相比，本发明未采用硝酸、硫酸、乙酸、氟磺酸等强酸体系，生产工艺之环境责任小，无需加热且仅在常温进行，能直接利用自然界普遍之可见光资源，以廉价易得之亚硝酸盐为硝化试剂，条件温和且选择性高，符合现代绿色化学的要求。
Description
技术领域
本发明属于光催化有机合成和精细化工技术领域，具体为一种光催化选择性硝化溴代苯酚的方法。
背景技术
赋予硝基官能团的溴代酚类中间体，经醚化、偶联或还原等反应转化为若干具有药理活性的终端产品。例如对位硝化的2-溴-4硝基苯酚，可制成以醚键连接含氟烷基的杀虫剂、连接氮杂环的糖尿病肽酶抑制剂，脱溴引入炔基的细胞毒素抑制剂等，邻位硝化的2-溴-6硝基苯酚经还原、偶联等反应得到3-氨基-2-羟基联苯-3-羧酸，属于血小板生成素受体激动剂-艾曲波帕的关键中间体，以及间位硝化的3-溴-5硝基苯酚以醚键连接苄基得到3-溴-5-硝基苯基苄基醚，能用于合成抗癌先导化合物自溶霉素。
向溴代酚引入硝基官能团的工艺，可借鉴参考其他卤代苯酚的硝化方法，一般采用硝酸硝化的工艺。1926年Herbert Henry Hodgson 和Francis Harry Moor最早使用发烟硫酸与硝酸钠硝化3-溴苯酚，得到3-溴-4硝基苯酚和3-溴-6-硝基苯酚（Herbert HenryHodgson and Francis Harry Moor. The Nitration of m-Bromophenol. Journal ofthe Chemical Society,1926,129, 155-161）；Robin G. Clewley等以硝酸和三氟乙酸酐硝化对溴苯酚，在氯仿中零下40℃反应得到4-溴-2-硝基苯酚，产率仅有25%（Robin G.Clewley, Gordon G. Cross, Alfred Fischer, George N. Henderson. Formation of4-Halo-4-nitrocyclohexa-2,5-dienones on nitration of p-halophenols and p-halophenyl acetates[J]. Tetrahedron, 1989, 45(5):1299-1310）；张耕等以硝酸和乙酸混合硝化，在冰水浴中使对溴苯酚转化为4-溴-2-硝基苯酚，产率提高到93%（张耕. 噻吩酮类及苯并噁嗪类化合物的合成研究[D]. 湘潭大学2014）。上述的硝酸硝化工艺流程较短、原理简单，但普遍采用强腐蚀或强氧化性酸，使用时容易造成一定的设备损失，也会引起严重的环境污染问题。
除硝酸之外，硝酸盐也是一种常用的硝基源。例如施敏等以硝酸铁混合65%硝酸为硝化剂，对溴苯酚在四氢呋喃中常温反应10h转化为2-硝基-4-溴苯酚，产率为66%，另有2,4-二溴-6-硝基苯酚、2-溴-4硝基苯酚及4-硝基苯酚等副产物（施敏, 尹万坡. 使用金属盐催化苯酚类及苯醚类化合物的硝化方法[P], CN 1709856 A,2005）；Hussni A. Muathen亦以硝酸铋和亚硫酰氯为硝化剂，使邻溴苯酚转化为52%的2-溴-4硝基苯酚和22%的2-溴-6硝基苯酚（Hussni A. Muathen. Selective nitration of aromatic compoundswithbismuth subnitrate and thionyl Chloride[J], Molecules, 2003, 8, 593-598）；V. Anuradha等优选硝酸镍为硝化剂，对甲苯磺酸为催化剂，使对溴苯酚在丙酮中常温反应1h得到4-溴-2-硝基苯酚，产率为78%（V. Anuradha, P. V. Srinivas, P. Aparnaand J.MadhusudanaRao. p -Toluenesulfonic acid catalyzed regiospecific nitration ofphenols with metal nitrates[J]. Tetrahedron Letters, 2006, 47(28):4933-4935）；K. Amani和F.Maleki以杂多酸为催化剂、硝酸铁为硝基源，2-溴苯酚在二氯甲烷中常温反应7.5～8.5h，得到60%的2-溴-4硝基苯酚和30%的2-溴-6硝基苯酚（K. Amani, F. Maleki.Catalytic effects of some keggin-type heteropolyacids andpolyoxometalates onselective nitration of phenols[J]. Journal of the IranianChemical Society,2007, 4 :238-243）；邓清海等以硫酸铜为催化剂、硝酸胍等为硝基源，与三甲基氯硅烷等在乙腈溶液中常温硝化，能使46%的对溴苯酚转化为4-溴-2-硝基苯酚（邓清海, 李思源,关振宇. 一种芳基酚类或芳基醚类衍生物的硝化方法[P], CN110590557A. 2019）。本质上，这些反应的机理仍然是依靠强酸或者强酸性催化剂获得硝酰正离子的亲电取代反应，且反应工艺中专一定位溴代硝基苯酚的选择性较低。
利用紫外光、可见光在内的多种光源，借助光子能量驱动有机合成，可以将一些苛刻条件下发生的化学反应转化为温和的环境下进行，但是只有极少部分关于光催化硝化的研究。例如王治明等以邻甲基苯甲酸为原料，亚硝酸钠、亚硝酸钾等亚硝酸盐为硝化试剂，乙腈、二氯乙烷等有机溶剂和水为混合试剂，以依红Y、吖啶盐等光敏剂负载的Fe3O4磁性纳米颗粒为光催化剂，波长范围在390～540nm可见光的催化下得到3,5-二硝基-2-甲基苯甲酸，最优条件下硝化产物的收率达到98%（王治明,杨健国,王磊,陈仁尔,马永敏. 一种3,5-二硝基-2-甲基苯甲酸的制备方法[P]. CN113149845A,2021）；Zhong等以环己烷为原料，采用300W高压汞灯作为光源，浓硝酸为硝化剂，在环己烷/硝酸双相体系中进行硝化转化率为22%、选择性为87%（Wenzhou Zhong, Liqiu Mao, Wenjun Yi,GouqiangZou, YongqiangLi, Dulin Yin. Highly efficient light-driven HNO3nitration–oxidation ofcyclohexane to co-productnitrocyclohexane and adipic acid in a biphasicsystem[J]. Research on ChemicalIntermediates, 2016, 42:461-470）。然而直至目前尚未有报道有一种光催化体系，能选择性合成专一定位的硝化溴代苯酚。
发明内容
本发明为了克服现有溴代苯酚硝化工艺的不足，提供了一种光催化选择性硝化溴代苯酚的方法，该方法无任何强酸或强酸性添加剂，仅需常温光照反应，操作简单，条件温和，方法新颖，选择性高。
为实现上述目的，本发明所采用以下技术方案：一种光催化选择性硝化溴代苯酚的方法，以二溴苯酚为原料，有机溶剂和水为混合溶剂，银胍/g-C3N4为催化剂，亚硝酸盐为硝化试剂，可见光下进行催化反应，反应结束后进行后处理得到产品溴代硝基苯酚。
具体步骤如下：
（1）制备银胍/g-C3N4：2g g-C3N4和150 mL乙腈混合，经80～100KHz超声处理0.5～2h，加入3.4～4.2mL单氰胺，与g-C3N4末端氨基反应生成胍基，加热回流24～48h后，过滤干燥得到胍/g-C3N4；0.4～0.9g硝酸银溶解于50 mL无水乙醇中，将得到的胍/g-C3N4加入到硝酸银的无水乙醇溶液，利用胍基与金属的螯合作用，避光加热回流8～12h，过滤洗去未反应的Ag+，将滤饼置于150W～300W氙灯下光照0.5～1h后，过滤干燥得到银胍/g-C3N4；
（2）光催化选择性硝化溴代苯酚：将0.05～0.2g银胍/g-C3N4催化剂和0.2g二溴苯酚在乙腈溶剂中搅拌0.5h，开启150W～300W氙灯光源，向溶液中滴加0.1mol/L亚硝酸盐水溶液16～32mL，控制滴加速度为6～10 mL/h，滴加完毕后常温继续搅拌3～5h，反应结束后减压蒸馏除去溶剂和水，所得产物用10 mL二氯甲烷萃取，以液相色谱分析并计算溴代硝基苯酚的产率。
所述步骤（2）中二溴苯酚为2,4-二溴苯酚、2,6-二溴苯酚或3,5-二溴苯酚中的任意一种。
所述步骤（2）中亚硝酸盐为亚硝酸钠或亚硝酸钾。
所述的液相色谱采用为标准的ODS C-18色谱柱，柱温35℃，流动相为体积比为25/75的乙腈/水，流速0.35 ml/min，紫外检测波长为260nm，原料及产物变化用常规的面积归一化法计算。
二溴苯酚在被硝化时还保留一个溴、没有彻底被替换，而且硝基引入到指定专一位置，可称之为选择性硝化。以往单溴苯酚的硝化反应，硝基引入的位置不确定，例如2-溴苯酚的硝化，同时得到2溴-4硝基和2溴-6硝基苯酚。本发明双溴苯酚的其中一个溴被定位替换成硝基，产物比较单一，相对于现有工艺的选择性比较好。本发明所述反应原理如下：
本发明的有益效果：与溴代苯酚的传统硝化工艺相比，本发明未采用硝酸、硫酸、乙酸、氟磺酸等强酸体系，生产工艺环境责任小，无需加热且仅在常温进行，能直接利用自然界普遍可见光资源，以廉价易得的亚硝酸盐为硝化试剂，所得溴代硝基苯酚的产品单一、选择性高，符合现代绿色化学的要求。
附图说明
图1为实施例1中所得银胍/g-C3N4的SEM-EDX谱图。从谱图中可以清楚的看到有银元素颗粒分散到褶皱的纳米片上，说明银已负载到胍基g-C3N4；
图2为实施例1中所得银胍/g-C3N4与常规银/g-C3N4用ICP-OES测试的金属含量，比较两个数据发现，相同条件下g-C3N4对银离子的负载含量比胍基g-C3N4减少了约68%，证明胍基g-C3N4与一般g-C3N4的显著不同；
图3为g-C3N4和实施例1中所得银胍/g-C3N4的FT-IR谱图，从图中可以看出，两种物质的吸收峰大致相同，其中806cm-1归属于三嗪环平面外的弯曲振动，特征吸收峰位于1200～1700cm-1归属于C－N杂环伸缩振动，3000～3500cm-1之间的吸收峰为N－H的伸缩振动，对比纯g-C3N4发现N－H伸缩振动明显增强，这主要是来自于银胍/g-C3N4的N－H，说明胍基与g-C3N4成功复合在一起；
图4为g-C3N4和实施例1中所得银胍/g-C3N4的UV-Vis谱图，从图中可以看出g-C3N4和银胍/g-C3N4在200～450nm有吸收，银胍/g-C3N4的吸收边缘相较于纯g-C3N4略发生了红移, 计算后银胍/g-C3N4的带隙值（Eg）为2.57eV，小于纯g-C3N4的带隙值Eg（2.69eV），说明银胍/g-C3N4可以吸收更多的光子，提高了对可见光的利用率。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例；基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
除非另有定义，所有在此使用的技术和科学术语，和本发明所属领域内的技术人员所通常理解的意思相同，在此公开引用及他们引用的材料都将以引用的方式被并入。
本领域技术人员意识到的通过常规实验就能了解到的描述的特定实施方案的等同技术，都将包含在本申请中。
下述实施例中的实验方法，如无特殊说明，均为常规方法。下述实施例中所用的仪器设备，如无特殊说明，均为实验室常规仪器设备；下述实施例中所用的实验材料，如无特殊说明，均为由常规生化试剂商店购买得到的。
实施例1：一种光催化选择性硝化溴代苯酚的方法，以二溴苯酚为原料，有机溶剂和水为混合溶剂，银胍/g-C3N4为催化剂，亚硝酸盐为硝化试剂，可见光下进行催化反应，反应结束后进行后处理得到产品溴代硝基苯酚。
具体步骤如下：
步骤（1）：称取2g g-C3N4和150 mL乙腈，经90KHz超声处理0.5h，加入4.2mL单氰胺与g-C3N4末端氨基反应生成胍基，加热回流36h后，过滤干燥得到胍/g-C3N4，加入到0.9g硝酸银和50 mL无水乙醇中，利用胍基与金属的螯合作用，避光加热回流8h，过滤洗去未反应的Ag+，将滤饼置于250W氙灯下光照0.5h后，过滤干燥得到银胍/g-C3N4；
步骤（2）：将0.2g银胍/g-C3N4催化剂和0.2g 2,6-二溴苯酚在乙腈溶剂中搅拌0.5h，开启250W氙灯光源，向溶液中滴加24mL的0.1mol/L亚硝酸钾水溶液，用注射泵控制滴加速度为10 mL/h，完毕后常温继续搅拌4h，反应结束后减压蒸馏除去溶剂和水，所得产物用10 mL二氯甲烷萃取，以液相色谱分析并计算2-溴-6硝基苯酚产率88%。反应方程式如下所示：
。
实施例2：步骤（1）：称取2g g-C3N4和150 mL乙腈，经100KHz超声处理2h，加入3.8mL单氰胺与g-C3N4末端氨基反应生成胍基，加热回流48h后，过滤干燥得到胍/g-C3N4，加入到0.7g硝酸银和50 mL无水乙醇中，利用胍基与金属的螯合作用，避光加热回流12h，过滤洗去未反应的Ag+，将滤饼置于300W氙灯下光照1h后，过滤干燥得到银胍/g-C3N4；
步骤（2）：将0.1g银胍/g-C3N4催化剂和0.2g 2,4-二溴苯酚在乙腈溶剂中搅拌0.5h，开启300W氙灯光源，向溶液中滴加32mL的0.1mol/L亚硝酸钾水溶液，用注射泵控制滴加速度为6 mL/h，完毕后常温继续搅拌5h，反应结束后减压蒸馏除去溶剂和水，所得产物用10 mL二氯甲烷萃取，以液相色谱分析并计算2-溴-4硝基苯酚产率93%。反应方程式如下所示：
。
实施例3：步骤（1）：称取2g g-C3N4和150 mL乙腈，经80KHz超声处理1h，加入3.4mL单氰胺与g-C3N4末端氨基反应生成胍基，加热回流24h后，过滤干燥得到胍/g-C3N4，加入到0.4g硝酸银和50 mL无水乙醇中，利用胍基与金属的螯合作用，避光加热回流10h，过滤洗去未反应的Ag+，将滤饼置于150W氙灯下光照1h后，过滤干燥得到银胍/g-C3N4；
步骤（2）：将0.05g银胍/g-C3N4催化剂和0.2g3,5-二溴苯酚在乙腈溶剂中搅拌0.5h，开启150W氙灯光源，向溶液中滴加16mL的0.1mol/L亚硝酸钠水溶液，用注射泵控制滴加速度为8 mL/h，完毕后常温继续搅拌3h，反应结束后减压蒸馏除去溶剂和水，所得产物用10 mL二氯甲烷萃取，以液相色谱分析并计算3-溴-5硝基苯酚产率85%。反应方程式如下所示：
。
氙灯释放的光谱几乎和太阳光一样，因而公认在实验室中常采用氙灯作为模拟太阳光等可见光的一种稳定光源。本发明即选用氙灯作为可见光光源进行光催化选择性硝化溴代苯酚实验。
根据上述实施例3，分别做无光和无催化剂的对照试验如下：
对照实例1：无光对照实验
步骤（1）：称取2g g-C3N4和150 mL乙腈，经80KHz超声处理1h，加入3.4mL单氰胺与g-C3N4末端氨基反应生成胍基，加热回流24h后，过滤干燥得到胍/g-C3N4，加入到0.4g硝酸银和50 mL无水乙醇中，利用胍基与金属的螯合作用，避光加热回流10h，过滤洗去未反应的Ag+，将滤饼置于150W氙灯下光照1h后，过滤干燥得到银胍/g-C3N4；
步骤（2）：将0.05g银胍/g-C3N4催化剂和0.2g3,5-二溴苯酚在乙腈溶剂中搅拌0.5h，在暗室中，向溶液中滴加16mL的0.1mol/L亚硝酸钠水溶液，用注射泵控制滴加速度为8mL/h，完毕后常温继续搅拌3h，反应结束后减压蒸馏除去溶剂和水，所得产物用10 mL二氯甲烷萃取，以液相色谱分析发现并未测得有产物3-溴-5硝基苯酚的存在。
对照实例2：无催化剂对照实验
步骤：将0.2g3,5-二溴苯酚在乙腈溶剂中搅拌0.5h，开启150W氙灯光源，向溶液中滴加16mL的0.1mol/L亚硝酸钠水溶液，用注射泵控制滴加速度为8 mL/h，完毕后常温继续搅拌3h，反应结束后减压蒸馏除去溶剂和水，所得产物用10 mL二氯甲烷萃取，以液相色谱分析并计算3-溴-5硝基苯酚产率19%。
根据对照实例1和对照实例2可以看出分别在无光和无催化剂条件下，目标产物产率较低甚至没有，这充分说明本发明所述催化剂及光催化硝化方法的优越性。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (3)
1.一种光催化选择性硝化溴代苯酚的方法，其特征在于：以二溴苯酚为原料，有机溶剂和水为混合溶剂，银胍/g-C3N4为催化剂，亚硝酸盐为硝化试剂，可见光下进行催化反应，反应结束后进行后处理得到产品溴代硝基苯酚；
具体步骤如下：
（1）制备银胍/g-C3N4：2g g-C3N4和150 mL乙腈混合，经80～100KHz超声处理0.5～2h，加入3.4～4.2mL单氰胺，与g-C3N4末端氨基反应生成胍基，加热回流24～48h后，过滤干燥得到胍/g-C3N4；0.4～0.9g硝酸银溶解于50 mL无水乙醇中，将得到的胍/g-C3N4加入到硝酸银的无水乙醇溶液，利用胍基与金属的螯合作用，避光加热回流8～12h，过滤洗去未反应的Ag+，将滤饼置于150W～300W氙灯下光照0.5～1h后，过滤干燥得到银胍/g-C3N4；
（2）光催化选择性硝化溴代苯酚：将0.05～0.2g银胍/g-C3N4催化剂和0.2g二溴苯酚在乙腈溶剂中搅拌0.5h，开启150W～300W氙灯光源，向溶液中滴加0.1mol/L亚硝酸盐水溶液16～32mL，控制滴加速度为6～10 mL/h，滴加完毕后常温继续搅拌3～5h，反应结束后减压蒸馏除去溶剂和水，所得产物用10 mL二氯甲烷萃取，以液相色谱分析并计算溴代硝基苯酚的产率；
所述步骤（2）中二溴苯酚为2,4-二溴苯酚、2,6-二溴苯酚或3,5-二溴苯酚中的任意一种。
2.根据权利要求1所述的一种光催化选择性硝化溴代苯酚的方法，其特征在于：所述步骤（2）中亚硝酸盐为亚硝酸钠或亚硝酸钾。
3.根据权利要求1所述的一种光催化选择性硝化溴代苯酚的方法，其特征在于：所述液相色谱为标准的ODS C-18色谱柱，柱温35℃，流动相为体积比25/75的乙腈/水，流速0.35ml/min，紫外检测波长为260nm，原料及产物变化用常规面积归一化法计算。
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