CN108949158A - 一种含吩噻嗪二苯酮类发光材料及其合成方法和应用 - Google Patents
一种含吩噻嗪二苯酮类发光材料及其合成方法和应用 Download PDFInfo
- Publication number
- CN108949158A CN108949158A CN201811035590.6A CN201811035590A CN108949158A CN 108949158 A CN108949158 A CN 108949158A CN 201811035590 A CN201811035590 A CN 201811035590A CN 108949158 A CN108949158 A CN 108949158A
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- China
- Prior art keywords
- phenothiazinyl
- derivative
- phenthazine
- benzophenone
- luminescent material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000008366 benzophenones Chemical class 0.000 title claims abstract description 29
- 239000012965 benzophenone Substances 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000010189 synthetic method Methods 0.000 title claims abstract description 14
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 claims abstract description 25
- 238000001514 detection method Methods 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003384 imaging method Methods 0.000 claims abstract description 8
- -1 nitro, amino Chemical group 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 229910052740 iodine Inorganic materials 0.000 claims description 13
- 239000011630 iodine Substances 0.000 claims description 13
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 12
- 150000001451 organic peroxides Chemical class 0.000 claims description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 10
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical group 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 claims description 4
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 3
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 238000006887 Ullmann reaction Methods 0.000 claims 3
- VXMAETDNBRYZJO-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)C1=CC=CC=C1.[I] Chemical class C(C1=CC=CC=C1)(=O)C1=CC=CC=C1.[I] VXMAETDNBRYZJO-UHFFFAOYSA-N 0.000 claims 1
- 241001597008 Nomeidae Species 0.000 claims 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- 239000004327 boric acid Substances 0.000 claims 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 abstract description 16
- 238000002189 fluorescence spectrum Methods 0.000 abstract description 10
- 230000004044 response Effects 0.000 abstract description 8
- 230000008859 change Effects 0.000 abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 150000003457 sulfones Chemical class 0.000 abstract description 2
- 150000003462 sulfoxides Chemical class 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- 239000000047 product Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- HKCNCNXZAZPKDZ-UHFFFAOYSA-N (4,4-difluorocyclohexa-1,5-dien-1-yl)-phenylmethanone Chemical compound C1=CC(F)(F)CC=C1C(=O)C1=CC=CC=C1 HKCNCNXZAZPKDZ-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- QERCGLJWOBWUSQ-UHFFFAOYSA-N C1=CC=C(C(=C1)C(=O)C2=CC=C(C=C2)C3=C4C(=CC=C3)SC5=CC=CC=C5N4)I Chemical compound C1=CC=C(C(=C1)C(=O)C2=CC=C(C=C2)C3=C4C(=CC=C3)SC5=CC=CC=C5N4)I QERCGLJWOBWUSQ-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 239000002360 explosive Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 0 *c(cc1)ccc1C(c1ccc(*)cc1)=O Chemical compound *c(cc1)ccc1C(c1ccc(*)cc1)=O 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 238000003809 water extraction Methods 0.000 description 2
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- UCCUXODGPMAHRL-UHFFFAOYSA-N 1-bromo-4-iodobenzene Chemical compound BrC1=CC=C(I)C=C1 UCCUXODGPMAHRL-UHFFFAOYSA-N 0.000 description 1
- ZZPNDIHOQDQVNU-UHFFFAOYSA-N 2-hydroxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OB(O)OC1(C)C ZZPNDIHOQDQVNU-UHFFFAOYSA-N 0.000 description 1
- CZKLEJHVLCMVQR-UHFFFAOYSA-N 4-fluorobenzoyl chloride Chemical compound FC1=CC=C(C(Cl)=O)C=C1 CZKLEJHVLCMVQR-UHFFFAOYSA-N 0.000 description 1
- NJAKCIUOTIPYED-UHFFFAOYSA-N 4-iodobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(I)C=C1 NJAKCIUOTIPYED-UHFFFAOYSA-N 0.000 description 1
- 206010006784 Burning sensation Diseases 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 208000000059 Dyspnea Diseases 0.000 description 1
- 206010013975 Dyspnoeas Diseases 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 206010030113 Oedema Diseases 0.000 description 1
- 206010035664 Pneumonia Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 206010037423 Pulmonary oedema Diseases 0.000 description 1
- 208000005392 Spasm Diseases 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- 206010047924 Wheezing Diseases 0.000 description 1
- FDQBNEUJUWUWKB-UHFFFAOYSA-N [4-(10H-phenothiazin-1-yl)phenyl]-(4-pyren-1-ylphenyl)methanone Chemical compound C1=CC=C2C(=C1)NC3=C(C=CC=C3S2)C4=CC=C(C=C4)C(=O)C5=CC=C(C=C5)C6=C7C=CC8=CC=CC9=C8C7=C(C=C9)C=C6 FDQBNEUJUWUWKB-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 208000030961 allergic reaction Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- RANKIEGFAHRPKF-UHFFFAOYSA-N diphenylmethanone;piperazine Chemical class C1CNCCN1.C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RANKIEGFAHRPKF-UHFFFAOYSA-N 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 210000000867 larynx Anatomy 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- SFDJOSRHYKHMOK-UHFFFAOYSA-N nitramide Chemical group N[N+]([O-])=O SFDJOSRHYKHMOK-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-BJUDXGSMSA-N oxygen-15 atom Chemical compound [15O] QVGXLLKOCUKJST-BJUDXGSMSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 208000005333 pulmonary edema Diseases 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000013102 re-test Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 208000013220 shortness of breath Diseases 0.000 description 1
- 230000037384 skin absorption Effects 0.000 description 1
- 231100000274 skin absorption Toxicity 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
- C07D279/24—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom with hydrocarbon radicals, substituted by amino radicals, attached to the ring nitrogen atom
- C07D279/26—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom with hydrocarbon radicals, substituted by amino radicals, attached to the ring nitrogen atom without other substituents attached to the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing aromatic rings
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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Abstract
本发明公开了一种含吩噻嗪二苯酮类发光材料及其合成方法和应用，发光材料中包含的吩噻嗪基上的硫原子本身在过氧自由基或单线态氧下易被氧化成亚砜或砜，导致整个分子的发光性质发生很大的改变，裸眼轻易识别，还可通过荧光光谱的变化确定过氧化物的浓度，实现更为精确的检测。本发明的合成方法工艺简单，容易纯化，所合成的发光材料具有高的荧光量子效率，对过氧化自由基具有特异性响应，吩噻嗪基团易被活性氧自由基、单线态氧氧化改变其发光性质，适用于化学生物检测、生物成像以及防伪领域。
Description
技术领域
本发明涉及新材料领域，特别是含有吩噻嗪基的新型有机发光材料及其合成方法，以及在化学过氧化物检测领域的应用。
背景技术
有机过氧化物(Organic Peroxides)是指化学结构中存在二价-O-O-结构的液态或固态有机物，包括有机过氧化物的混合物。有机过氧化物化学活性高，对热、撞击或摩擦敏感，可发生放热自加速爆炸分解，易与其他物质发生危险反应。许多有机化合物在储存的过程中会产生过氧化物，过氧化物中都含有过氧化自由基(-O-O-)，过氧键的结合力较弱，仅需少量的能量即可发生断裂，因此过氧基是极不稳定的结构，对热、冲击、振动或者摩擦等外界刺激均极为敏感，轻微的外界作用便可使其分解。有机过氧化物分解时，分解反应放热速度远远大于周围环境的散热速度，在极短的时间内产生大量的热量而产生爆炸。同时，有机过氧化物过氧键的活化能低于一般的爆炸物，约为80～160kj/mol，其自燃温度较低，因此大多数有机过氧化物易燃易爆，特别是在密闭空间中存放、使用时，极易受热燃烧甚至爆炸。过氧化物被人体吸收后(吸入、口服、皮肤吸收等)，对眼睛、皮肤、粘膜及上呼吸道有刺激作用。吸入后可引起喉、支气管的炎症、水肿、痉挛及化学性肺炎、肺水肿。接触后可引起灼烧感、咳嗽、喘息、气短、头痛、恶心及呕吐等，可引起过敏反应。由此，研究开发精确有效的检测过氧化物浓度的方法，将有助于预防过氧化物积累对人类活动产生危害。
以醚类有机试剂为例，久藏的醚类(乙醚、二氧六环等)中会产生过氧化物，当过氧化物积累到一定量时，将会存在爆炸的可能。传统的检测醚类溶剂中是否产生过氧化物的方法是在适当浓度的淀粉碘化钾溶液中滴加乙醚溶液并振荡，根据水层是否变蓝来定性判断过氧化物的有无。若需进一步确认过氧化物的浓度，仍需要通过硫代硫酸钠溶液滴定。此种检测手段较为粗糙，检测限较高，灵敏度较差，有待进一步改进。
发明内容
本发明的目的是提供一种对过氧化自由基、单线态氧等具有特异性响应的含吩噻嗪二苯酮类发光材料。
本发明的另一个目的是提供上述含吩噻嗪二苯酮类发光材料的合成方法，这些方法工艺简单，产率高，易于纯化，并可通过引入不同官能团进而调节终产物的发光波长、对过氧化自由基响应快慢等性能。
本发明的第三个目的是将上述含吩噻嗪二苯酮类发光材料应用于化学检测、生物成像、防伪等领域，主要是用于有机过氧化物的检测。
为实现上述目的，本发明提供一种含吩噻嗪二苯酮类发光材料，其分子通式如通式(1)所示：
通式(1)：
Pz为含有吩噻嗪基官能团，R与Pz相同或不同，R选自烷基、卤素、烷氧基、硝基、氨基、醛基、氰基、芳香环或芳香杂环取代基。
所述的含吩噻嗪二苯酮类发光材料的合成方法，其特征在于包括：
方法(1)将吩噻嗪基衍生物与一端或两端含有氟的二苯酮衍生物通过偶联反应得到目标产物；
方法(2)将吩噻嗪基衍生物与一端或两端含有溴或碘的二苯酮衍生物通过乌尔曼反应得到目标产物；
方法(3)将对吩噻嗪基苯硼酸衍生物与一端或两端还有溴或碘的二苯酮衍生物通过Suzuki偶联反应得到目标产物。
上述含吩噻嗪二苯酮类发光材料应用于化学检测、生物成像、防伪领域。
本发明的含吩噻嗪二苯酮类发光材料是具有优异发光性能的有机发光材料，其中给受体基团的合理匹配能降低分子本身的单线态-三线态能极差(ΔEST)，有利于产生热激活延迟荧光，对氧气具有特异性响应，而吩噻嗪基上的硫原子本身在过氧自由基或单线态氧下易被氧化成亚砜或砜，导致整个分子的发光性质发生很大的改变，裸眼轻易识别，还可通过荧光光谱的变化确定过氧化物的浓度，实现更为精确的检测。
本发明的合成方法工艺简单，容易纯化，所合成的发光材料具有高的荧光量子效率，对过氧化自由基具有特异性响应，吩噻嗪基团易被活性氧自由基、单线态氧氧化改变其发光性质，适用于化学生物检测、生物成像以及防伪领域。
为了能更进一步阐述本发明的特征及技术内容，请参阅以下有关本发明的附图，但附图仅为提供参考与说明，并非用于对本发明加以限制。
附图说明
下面结合附图，详细描述本发明的具体实施方式，以便能更清晰地表达本发明的技术方案及其它有益效果。
附图中，
图1为本发明实施例1-5产物的固体荧光照片；
图2为本发明实施例1产物的甲苯溶液通氧前后的荧光发射光谱；
图3为本发明实施例1产物的甲苯溶液通氧前后的荧光寿命变化；
图4为本发明实施例1产物的乙醚(久藏)溶液随放置时间增长的荧光光谱变化。
具体实施方式
本发明的含有吩噻嗪基的有机发光材料其分子通式如通式(1)所示：
通式(1)：
Pz为含有吩噻嗪基官能团，R可以与Pz相同，也可以不同，R可以为烷基、卤素、烷氧基、硝基、氨基、醛基、氰基、芳香环或芳香杂环取代基。
优选的，其中所述含有吩噻嗪基官能团Pz选自以下结构：
其结构中R1可以与R2相同，R1和R2可以为氢、烷基、卤素、烷氧基、硝基、氨基、醛基、氰基、苯基、萘基、蒽基、咔唑基、二苯胺基或吩噻嗪基。
优选的，通式(1)中，R可以为烷基、卤素、烷氧基、硝基、氨基、醛基、氰基、芳香环或芳香杂环取代基，其中R为芳香环或芳香杂环取代基时选自以下结构：
其结构中R3可以与R4相同，也可以不同，R3和R4可以为氢、烷基、卤素、烷氧基、硝基、氨基、醛基、氰基、苯基、萘基、蒽基、咔唑基、二苯胺基或吩噻嗪基。
所述的含有吩噻嗪基二苯酮类有机发光材料【通式(1)】的几类合成方法：
方法(1)将吩噻嗪基衍生物与一端或两端含有氟的二苯酮衍生物通过偶联反应得到目标产物。优选由以下方法实现：提供吩噻嗪基衍生物与含氟的二苯酮衍生物，在N,N-二甲基甲酰胺溶液中，以叔丁醇钾为碱，加热回流得到目标产物。
方法(2)将吩噻嗪基衍生物与一端或两端含有溴或碘的二苯酮衍生物通过乌尔曼反应得到目标产物。优选由以下方法实现：提供吩噻嗪基衍生物、含溴或碘的二苯酮衍生物、18-冠醚-6、邻菲罗啉以及碳酸钾，在干燥的N,N-二甲基甲酰胺溶液中，以碘化亚铜为催化剂，加热回流得到目标产物。
方法(3)将对吩噻嗪基苯硼酸衍生物与一端或两端还有溴或碘的二苯酮衍生物通过Suzuki偶联反应得到目标产物。优选由以下方法实现：提供对吩噻嗪基本硼酸酯衍生物与含溴或碘的二苯酮衍生物、碳酸钾水溶液及相转移剂，在干燥的四氢呋喃溶液中，以四三苯基膦钯为催化剂，加热回流得到目标产物。
本发明的合成方法工艺简单，容易纯化，所合成的发光材料具有高的荧光量子效率，对过氧化自由基具有特异性响应，适用于有机过氧化物的检测。此外，本发明的发光材料还对氧气、单线态氧等具有特异性响应，适用应用于化学生物检测，生物成像以及防伪等领域，例如作为检测剂应用于有机过氧化物的检测，或者是作为荧光探针应用于生物成像。
以下通过具体的实施例子对本发明作进一步的阐述，但本发明并不限于此特定例子。
实施例1：
(1)中间体【4,4-二氟二苯酮】的合成
将4-氟苯甲酰氯(5.00g，31.5mmol)加入250mL干燥三颈瓶中，再加入氟苯(7.58g，78.8mmol)，搅拌，加入无水氯化铝(12.6g，94.1mmol)，升温至40～50℃，反应5～6h。反应结束后，在三颈瓶中加入二氯甲烷50ml溶解，缓慢加入稀盐酸，搅拌至无沉淀。然后将反应液倒入分液漏斗，用二氯甲烷萃取3次，再用稀盐酸洗2～3次至水层变为无色。将有机层用无水硫酸钠干燥，过滤，滤液在旋转蒸发仪中旋干，得到白色固体5.73g。产率83.3％。
(2)中间体【4-氟-4’-吩噻嗪基二苯酮】的合成
将吩噻嗪(1.03g，11.5mmol)加入250mL三口瓶中，加入适量DMF，在氩气环境中加入NaH(0.41g,17.2mmol)。搅拌半小时后加入4,4-二氟二苯酮(2.50g，11.5mmol)，升温至110℃，反应12h。之后将反应液冷却，加入二氯甲烷和水萃取，用二氯甲烷萃取3次，再用水洗3次。将有机层用无水硫酸钠干燥，在旋转蒸发仪中旋干。然后利用硅胶柱层析的方法进行提纯，淋洗液为体积比1:2的二氯甲烷和正己烷的混合溶液。得黄白色固体1.32g，产率64.4％。
(3)目标产物实施例1的合成
参照实施例1的步骤(2)，利用4-氟-4’-吩噻嗪基二苯酮代替4,4-二氟二苯酮合成4-二苯基胺-4’-吩噻嗪基二苯酮。(产率为59.3％)1H NMR(500MHz,DMSO-d6)δ7.79–7.75(m,2H),7.69–7.65(m,2H),7.42–7.36(m,4H),7.33(dd,J＝7.6,1.5Hz,2H),7.30–7.26(m,2H),7.21–7.15(m,8H),7.09(td,J＝7.5,1.3Hz,2H),6.91–6.86(m,4H).
本实施例产物的甲苯溶液通氧前后的荧光发射光谱如图2所示。将实施例1的产物配成1*10^-5mol/L的甲苯溶液，在365纳米紫外光激发下采集其荧光发射光谱；然后对该溶液用氧气鼓泡15分钟后，在同样的条件下再测试其荧光发射光谱。经过氧气鼓泡后的溶液在长波方向的发射峰强度明显降低，说明实施例1的发光对氧气敏感，其发光过程涉及三线态激子的参与，氧气猝灭了三线态激子，导致其发光减弱。
本实施例产物的甲苯溶液通氧前后的荧光寿命变化如图3所示。通氧后实施例1产物的长寿命消失，长寿命组分被氧气猝灭，只剩下短寿命成分。
本实施例产物的乙醚(久藏)溶液随放置时间增长的荧光光谱变化如图4所示。实施例1的产物配成1*10^-5mol/L的乙醚溶液，在365纳米紫外光激发下采集其放置不同时间时的荧光发射光谱；溶液的荧光发射光谱中在480纳米左右会产生一个新的发射峰并且随着溶液放置时间增长越来越强，说明乙醚中的过氧化物将分子逐步氧化生成新产物后导致发光不断增强，以此可用来检测乙醚中是否含有过氧化物及其过氧化物的量。
实施例2：
(1)目标产物实施例2的合成
参照实施例1的步骤(2)，利用4-氟-4’-吩噻嗪基二苯酮代替4,4-二氟二苯酮合成4-咔唑基-4’-吩噻嗪基二苯酮。(产率为52.5％)1H NMR(300MHz,CDCl3)δ8.16-8.14(d,2H),8.05-8.03(d,2H),7.92-7.90(d,2H),7.72-7.70(d,2H),7.53-7.26(m,11H),7.25,7.21-7.10(t,5H).
实施例3：
(1)中间体【1-溴-4-吩噻嗪基苯】的合成
将吩噻嗪(3.00g,15.1mmol)和1-溴-4-碘苯(4.68g,16.6mmol)加入250mL三口瓶中，加入适量的DMF溶解，通氩气搅拌下分别加入一小勺碘化亚铜、18-冠醚-6及邻菲罗啉，搅拌均匀后再加入碳酸钾(6.51g,45.3mmol)，加热回流搅拌12h。冷却至室温，倒入冷水中，用二氯甲烷萃取3次，水洗2次，将有机层用无水硫酸钠干燥，在旋转蒸发仪中旋干。然后利用硅胶柱层析的方法进行提纯，淋洗液为体积比1:3的二氯甲烷和正己烷的混合溶液。得白色固体2.54g，产率47.6％。
(2)中间体【4-吩噻嗪基苯硼酸酯】的合成
将1-溴-4-吩噻嗪基苯(1.50g,4.2mmol)、联硼酸频那醇酯(2.15g,8.5mmol)和醋酸钾(1.25g,12.7mmol)加入250mL三口瓶中，加入适量的二氧六环溶解，升温至90℃，通氩气搅拌30min后加入一小勺Pd(dppf)Cl2，加热回流搅拌16h。将反应液转移到单口瓶，在旋转蒸发仪中旋干。然后利用硅胶柱层析的方法进行提纯，淋洗液为体积比1:3的二氯甲烷和正己烷的混合溶液。得白色固体1.03g，产率60.6％。
(3)中间体【4-氟-4’-碘二苯酮】的合成
将4-碘苯甲酰氯(5.00g，18.8mmol)加入250mL干燥三颈瓶中，再加入氟苯(5.41g，56.3mmol)，搅拌，加入无水氯化铝(3.88g，28.2mmol)，升温至40～50℃，反应5～6h。反应结束后，在三颈瓶中加入二氯甲烷50ml溶解，缓慢加入稀盐酸，搅拌至无沉淀。然后将反应液倒入分液漏斗，用二氯甲烷萃取3次，再用稀盐酸洗2～3次至水层变为无色。将有机层用无水硫酸钠干燥，过滤，滤液在旋转蒸发仪中旋干，得到黄白色固体5.06g。产率83％。
(4)中间体【4-氟-4’-苯吩噻嗪基二苯酮】的合成
将4-吩噻嗪基苯硼酸酯(1.44g，3.1mmol)、4-氟-4’-碘二苯酮(1.00g,3.1mmol)和碳酸钾(1.27g,9.2mmol)加入250mL三口瓶中，加入适量四氢呋喃，在氩气环境中加入一小勺四三苯基膦钯。升温至110℃，反应12h。之后将反应液冷却，加入二氯甲烷和水萃取，用二氯甲烷萃取3次，再用水洗3次。将有机层用无水硫酸钠干燥，在旋转蒸发仪中旋干。然后利用硅胶柱层析的方法进行提纯，淋洗液为体积比1:2的二氯甲烷和正己烷的混合溶液。得黄白色固体0.95g，产率65.4％。
(5)目标产物实施例3的合成
参照实施例1的步骤(2)，利用4-氟-4’-苯吩噻嗪基二苯酮代替4,4-二氟二苯酮合成4-咔唑基-4’-苯吩噻嗪基二苯酮。(产率为56.1％)
实施例4：
(1)中间体【4-碘-4’-吩噻嗪基二苯酮】的合成
参照实施例1的步骤(2)，利用4-氟-4’-碘二苯酮代替4,4-二氟二苯酮合成4-碘-4’-吩噻嗪基二苯酮。(产率为54.2％)
(2)目标产物实施例4的合成
参照实施例3的步骤(4)，利用4-碘-4’-吩噻嗪基二苯酮代替4-碘-4’-氟二苯酮，利用1-萘硼酸酯代替4-吩噻嗪基苯硼酸酯合成4-萘基-4’-吩噻嗪基二苯酮。(产率为60.3％)1H NMR(500MHz,CDCl3)δ7.98–7.88(m,7H),7.64–7.60(m,2H),7.58–7.50(m,2H),7.47(td,J＝7.0,1.3Hz,2H),7.33(dd,J＝7.7,1.5Hz,2H),7.30–7.27(m,2H),7.20(td,J＝7.8,1.5Hz,2H),7.10(t,J＝7.5Hz,2H),7.06–7.02(m,2H).
实施例5：
(1)目标产物实施例5的合成
参照实施例3的步骤(4)，利用4-碘-4’-吩噻嗪基二苯酮代替4-碘-4’-氟二苯酮，利用1-芘硼酸酯代替4-吩噻嗪基苯硼酸酯合成4-芘基-4’-吩噻嗪基二苯酮。(产率为60.3％)1H NMR(500MHz,CDCl3)δ8.28–8.16(m,4H),8.13(s,2H),8.09–7.95(m,7H),7.79–7.74(m,2H),7.32(ddd,J＝17.0,7.2,1.7Hz,4H),7.20(t,J＝7.4Hz,2H),7.14–7.00(m,4H).
本发明实施例1-5产物的固体荧光照片如图1所示。
表1:实施例中终产物在溶液和固体的最大荧光发射波长
注：固体的发射光谱由Shimadzu RF-5301PC荧光分光光度计测量
综上所述，本发明的合成方法工艺简单，容易纯化，所合成的发光材料具有高的荧光量子效率，对过氧化自由基具有特异性响应，适用于有机过氧化物的检测。此外，本发明的发光材料还对氧气、单线态氧等具有特异性响应，适用应用于化学生物检测，生物成像以及防伪等领域。以上所述，本领域的普通技术人员可以根据本发明的技术方案和技术构思作出其它各种相应的改变和变形，而所有这些改变和变形都应属于本发明权利要求的保护范围。
Claims (9)
1.一种含吩噻嗪二苯酮类发光材料，其分子通式如通式(1)所示：
通式(1)：
Pz为含有吩噻嗪基官能团，R与Pz相同或不同，R选自烷基、卤素、烷氧基、硝基、氨基、醛基、氰基、芳香环或芳香杂环取代基。
2.根据权利要求1所述的含吩噻嗪二苯酮类发光材料，其特征在于：所述含有吩噻嗪基官能团Pz选自以下结构：
其结构中R1与R2相同，R1和R2选自氢、烷基、卤素、烷氧基、硝基、氨基、醛基、氰基、苯基、萘基、蒽基、咔唑基、二苯胺基或吩噻嗪基。
3.根据权利要求1所述的含吩噻嗪二苯酮类发光材料，其特征在于：所述R为芳香环或芳香杂环取代基时选自以下结构：
其结构中R3与R4相同或不同，R3和R4选自氢、烷基、卤素、烷氧基、硝基、氨基、醛基、氰基、苯基、萘基、蒽基、咔唑基、二苯胺基或吩噻嗪基。
4.权利要求1、2或3所述的含吩噻嗪二苯酮类发光材料的合成方法，其特征在于包括：
方法(1)将吩噻嗪基衍生物与一端或两端含有氟的二苯酮衍生物通过偶联反应得到目标产物；
方法(2)将吩噻嗪基衍生物与一端或两端含有溴或碘的二苯酮衍生物通过乌尔曼反应得到目标产物；
方法(3)将对吩噻嗪基苯硼酸衍生物与一端或两端还有溴或碘的二苯酮衍生物通过Suzuki偶联反应得到目标产物。
5.根据权利要求4所述的合成方法，其特征在于：所述的方法(1)，吩噻嗪基衍生物与含氟的二苯酮衍生物的偶联反应由以下方法实现：提供吩噻嗪基衍生物与含氟的二苯酮衍生物，在N,N-二甲基甲酰胺溶液中，以叔丁醇钾为碱，加热回流得到目标产物。
6.根据权利要求4所述的合成方法，其特征在于：所述的方法(2)，吩噻嗪基衍生物与含溴或碘的二苯酮衍生物的乌尔曼反应由以下方法实现：提供吩噻嗪基衍生物、含溴或碘的二苯酮衍生物、18-冠醚-6、邻菲罗啉以及碳酸钾，在干燥的N,N-二甲基甲酰胺溶液中，以碘化亚铜为催化剂，加热回流得到目标产物。
7.根据权利要求4所述的合成方法，其特征在于：所述的方法(3)，对吩噻嗪基苯硼酸酯衍生物与含溴或碘的二苯酮衍生物的乌尔曼反应由以下方法实现：提供对吩噻嗪基本硼酸酯衍生物与含溴或碘的二苯酮衍生物、碳酸钾水溶液及相转移剂，在干燥的四氢呋喃溶液中，以四三苯基膦钯为催化剂，加热回流得到目标产物。
8.权利要求1、2或3所述的含吩噻嗪二苯酮类发光材料应用于化学检测、生物成像、防伪领域。
9.根据权利要求8所述的应用，其特征在于：所述的化学检测为有机过氧化物、氧气或单线态氧的检测。
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