CN115947711B - Photochemical caching agent and synthesis method thereof - Google Patents
Photochemical caching agent and synthesis method thereof Download PDFInfo
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- CN115947711B CN115947711B CN202211357622.0A CN202211357622A CN115947711B CN 115947711 B CN115947711 B CN 115947711B CN 202211357622 A CN202211357622 A CN 202211357622A CN 115947711 B CN115947711 B CN 115947711B
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- 238000001308 synthesis method Methods 0.000 title claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 150000008062 acetophenones Chemical class 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 6
- 238000006467 substitution reaction Methods 0.000 claims abstract description 6
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract 2
- -1 C1-C20 alkylbenzene Chemical group 0.000 claims description 74
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 60
- 239000002904 solvent Substances 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000003208 petroleum Substances 0.000 claims description 30
- 238000001914 filtration Methods 0.000 claims description 27
- 238000004440 column chromatography Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical group C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 12
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 238000004537 pulping Methods 0.000 claims description 9
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 8
- 125000001188 haloalkyl group Chemical group 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical group O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- BGPDQWZQYUDVCY-UHFFFAOYSA-N 2-methyl-n-(2-methylphenyl)prop-2-enamide Chemical compound CC(=C)C(=O)NC1=CC=CC=C1C BGPDQWZQYUDVCY-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 3
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims 4
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims 1
- 125000004641 (C1-C12) haloalkyl group Chemical group 0.000 claims 1
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims 1
- 239000012043 crude product Substances 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000000872 buffer Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 35
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 32
- 239000000203 mixture Substances 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- 125000004432 carbon atom Chemical group C* 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 16
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 16
- 125000003118 aryl group Chemical group 0.000 description 16
- 238000012512 characterization method Methods 0.000 description 16
- 125000001072 heteroaryl group Chemical group 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 9
- 125000003342 alkenyl group Chemical group 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 7
- 125000002252 acyl group Chemical group 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 125000003107 substituted aryl group Chemical group 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 5
- 125000005017 substituted alkenyl group Chemical group 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 150000001448 anilines Chemical class 0.000 description 4
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 4
- 239000006172 buffering agent Substances 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- FUQMPVPFVKIMMK-UHFFFAOYSA-N n-(2,2-diphenylethyl)aniline Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)CNC1=CC=CC=C1 FUQMPVPFVKIMMK-UHFFFAOYSA-N 0.000 description 4
- 238000006552 photochemical reaction Methods 0.000 description 4
- 238000010626 work up procedure Methods 0.000 description 4
- ILCZYZUBDFQDDB-UHFFFAOYSA-N 1-(4-bromophenyl)-2,2-dihydroxyethanone Chemical compound OC(O)C(=O)C1=CC=C(Br)C=C1 ILCZYZUBDFQDDB-UHFFFAOYSA-N 0.000 description 3
- VFIKEUWNHSLFPY-UHFFFAOYSA-N 1-(4-fluorophenyl)-2,2-dihydroxyethanone Chemical compound OC(O)C(=O)C1=CC=C(F)C=C1 VFIKEUWNHSLFPY-UHFFFAOYSA-N 0.000 description 3
- ZDPAWHACYDRYIW-UHFFFAOYSA-N 1-(4-fluorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(F)C=C1 ZDPAWHACYDRYIW-UHFFFAOYSA-N 0.000 description 3
- DNYMAUICCMLWCF-UHFFFAOYSA-N 2,2-dihydroxy-1-(4-phenylphenyl)ethanone Chemical compound C1=CC(C(=O)C(O)O)=CC=C1C1=CC=CC=C1 DNYMAUICCMLWCF-UHFFFAOYSA-N 0.000 description 3
- GVOIGFCWPBJXSM-UHFFFAOYSA-N 2,2-dihydroxy-1-[4-(trifluoromethyl)phenyl]ethanone Chemical compound OC(O)C(=O)C1=CC=C(C(F)(F)F)C=C1 GVOIGFCWPBJXSM-UHFFFAOYSA-N 0.000 description 3
- NBIBDIKAOBCFJN-UHFFFAOYSA-N 2,2-dihydroxy-1-phenylethanone Chemical compound OC(O)C(=O)C1=CC=CC=C1 NBIBDIKAOBCFJN-UHFFFAOYSA-N 0.000 description 3
- NOJRBLVRZRROHF-UHFFFAOYSA-N 2-ethyl-n,n-diphenylaniline Chemical compound CCC1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 NOJRBLVRZRROHF-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- LQKYCMRSWKQVBQ-UHFFFAOYSA-N n-dodecylaniline Chemical compound CCCCCCCCCCCCNC1=CC=CC=C1 LQKYCMRSWKQVBQ-UHFFFAOYSA-N 0.000 description 3
- 125000000547 substituted alkyl group Chemical group 0.000 description 3
- 125000006686 (C1-C24) alkyl group Chemical group 0.000 description 2
- HHAISVSEJFEWBZ-UHFFFAOYSA-N 1-[4-(trifluoromethyl)phenyl]ethanone Chemical compound CC(=O)C1=CC=C(C(F)(F)F)C=C1 HHAISVSEJFEWBZ-UHFFFAOYSA-N 0.000 description 2
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 2
- NMNXZIFOFHFWLO-UHFFFAOYSA-N C1COC(=C(O1)C2=CC=CC=C2)C3=CC=C(C=C3)N Chemical compound C1COC(=C(O1)C2=CC=CC=C2)C3=CC=C(C=C3)N NMNXZIFOFHFWLO-UHFFFAOYSA-N 0.000 description 2
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000002837 carbocyclic group Chemical group 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000891 luminescent agent Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 125000006682 monohaloalkyl group Chemical group 0.000 description 2
- 125000006574 non-aromatic ring group Chemical group 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 125000006684 polyhaloalkyl group Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- CJAAPVQEZPAQNI-UHFFFAOYSA-N (2-methylphenyl)methanamine Chemical compound CC1=CC=CC=C1CN CJAAPVQEZPAQNI-UHFFFAOYSA-N 0.000 description 1
- MSDQNIRGPBARGC-UHFFFAOYSA-N 1-(4-cyclohexylphenyl)ethanone Chemical compound C1=CC(C(=O)C)=CC=C1C1CCCCC1 MSDQNIRGPBARGC-UHFFFAOYSA-N 0.000 description 1
- UYFJYGWNYQCHOB-UHFFFAOYSA-N 1-(4-tert-butylphenyl)ethanone Chemical compound CC(=O)C1=CC=C(C(C)(C)C)C=C1 UYFJYGWNYQCHOB-UHFFFAOYSA-N 0.000 description 1
- QQLIGMASAVJVON-UHFFFAOYSA-N 1-naphthalen-1-ylethanone Chemical compound C1=CC=C2C(C(=O)C)=CC=CC2=C1 QQLIGMASAVJVON-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NLPHXWGWBKZSJC-UHFFFAOYSA-N 4-acetylbenzonitrile Chemical compound CC(=O)C1=CC=C(C#N)C=C1 NLPHXWGWBKZSJC-UHFFFAOYSA-N 0.000 description 1
- YQYGPGKTNQNXMH-UHFFFAOYSA-N 4-nitroacetophenone Chemical compound CC(=O)C1=CC=C([N+]([O-])=O)C=C1 YQYGPGKTNQNXMH-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005024 alkenyl aryl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000005018 aryl alkenyl group Chemical group 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000008282 halocarbons Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SKXBOHNVJVHVJX-UHFFFAOYSA-N n-docosylaniline Chemical compound CCCCCCCCCCCCCCCCCCCCCCNC1=CC=CC=C1 SKXBOHNVJVHVJX-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of photochemical long afterglow materials, and relates to a photochemical buffer agent and a synthesis method thereof. The synthesis method comprises the steps of oxidation, substitution, cyclization and the like, and the photochemical buffer agent with various chemical molecular structures can be designed and synthesized according to the needs by selecting acetophenone derivatives and aniline derivatives as raw materials and matching with the optimization of other technological parameters.
Description
Technical Field
The invention belongs to the field of photochemical long afterglow materials, and in particular relates to a photochemical buffering agent and a synthesis method thereof.
Background
Long-afterglow phosphors are a special class of phosphors that emit light for a long period of time after removal of the excitation source, typically with a luminescence lifetime of more than 100 ms. In recent decades, afterglow materials have been attracting more and more attention, because of their good performance, long afterglow luminescent materials have important application values in the fields of dim light illumination, display decoration, safety identification, emergency indication, biomedicine, life science, environmental engineering and the like.
In recent years, photochemically long afterglow materials have been developed by introducing photochemical reactions. Is favored by scientific researchers because of the unique lighting process. The general photochemical long afterglow material comprises a light absorber, a luminescent agent, a photochemical buffer agent and the like, wherein the photochemical buffer agent is a core component of the photochemical long afterglow material. The function of the photochemical buffer agent is mainly the conversion of photochemical energy, and unlike the luminescent agent with main functional site luminescence, the buffer agent molecule itself does not emit light or emits light very weakly, and the molecular structure generally does not contain a group or conjugated structure capable of directly emitting light. It assists in participating in the photochemical reaction, creating a bridge for energy exchange and storage between the luminescent and light absorbing agents, and in the photochemical reaction, through the reaction steps of addition, rearrangement or bond cleavage, the energy extraction process between the energy levels is activated.
Photochemical buffering agents are generally compounds containing olefinic double bonds that are capable of reacting with reactive oxygen species generated in a photochemical reaction, and the reaction product spontaneously cleaves and generates new species in an excited state. At present, the synthesis method of the photochemical buffer agent has few reports, a complete product supply chain is not formed in China, expensive photochemical buffer agent finished products can only be purchased from abroad when the photochemical long afterglow material is prepared, and because the design, production and transportation processes are quite time-consuming, only a small number of buffer agent finished products can be ordered each time, the cost of the whole preparation process is high, the types of the used buffer agent finished products are limited, and the development and application of the long afterglow material in a plurality of different fields are not facilitated, so that the development of a synthesis method capable of conveniently preparing the diversified photochemical buffer agent is urgently needed to reduce the preparation, research and development and use cost of the photochemical long afterglow material, and further the application field of the photochemical long afterglow material is widened.
Disclosure of Invention
In order to overcome the defects, the invention provides a photochemical caching agent and a synthesis method thereof.
In one aspect, the invention provides a method for synthesizing a photochemical buffer agent, which comprises the following steps:
(1) The acetophenone derivative I and inorganic oxide undergo oxidation reaction to obtain a compound II,
(2) The compound II and the aniline derivative III undergo substitution reaction to obtain a compound IV,
(3) ① In the presence of a catalyst, the compound IV and mercaptoethanol react to form a ring to obtain a target compound V,
Or ② in the presence of a catalyst, the compound IV and ethylene glycol undergo a cyclization reaction to obtain a target compound VI,
Wherein,
R 1 is hydrogen, nitro, cyano, hydroxy, acyl, sulfonic, halo, C1-C24 haloalkyl, C3-C10 cycloalkyl, C2-C20 alkenyl, C6-C20 aryl, or C1-C15 heteroaryl with N, O or S, or a combination thereof;
r 2 and R 3 are each independently hydrogen, C1-C24 alkyl, C6-C20 aryl or C1-C15 heteroaryl with N, O or S, or a combination thereof.
In the present invention, halogen is chlorine, fluorine, bromine or iodine, haloalkyl is a straight-chain, branched or cyclic saturated aliphatic halogenated hydrocarbon group, and haloalkyl includes monohaloalkyl and polyhaloalkyl.
In certain embodiments, the haloalkyl has 1 to 12 carbon atoms.
In certain embodiments, the haloalkyl has 1 to 6 carbon atoms.
In certain embodiments, haloalkyl is fluoroalkyl or bromoalkyl.
In the present invention, cycloalkyl is a saturated or unsaturated non-aromatic ring group.
In certain embodiments, the cycloalkyl group has 3 to 6 carbon atoms.
In the present invention, an alkenyl group is a straight or branched hydrocarbon having at least one double bond, and an alkenyl group includes a substituted alkenyl group or an unsubstituted alkenyl group, and a substituted alkenyl group includes an alkenyl aryl group or an aralkenyl group.
In certain embodiments, the alkenyl group has 2 to 10 carbon atoms.
In the present invention, the aryl group is an aromatic carbocyclic group having a single ring, multiple rings or multiple condensed rings, and the aryl group includes unsubstituted aryl groups and substituted aryl groups, and the substituents on the substituted aryl groups are nitro groups, cyano groups, hydroxyl groups, acyl groups, sulfonic groups, halogens, alkyl groups, or combinations thereof.
In certain embodiments, the aryl group has 6 to 14 carbon atoms.
In the present invention, heteroaryl is a monocyclic or polycyclic group comprising 1 to 4 heteroatoms selected from N, O or S, heteroaryl includes unsubstituted heteroaryl and substituted heteroaryl, the substituents on the substituted heteroaryl being nitro, cyano, hydroxy, acyl, sulfonic, halogen, alkyl, aryl, or combinations thereof.
In certain embodiments, the heteroaryl group has 6 to 14 carbon atoms and the heteroatom is nitrogen.
In the present invention, the alkyl group is a straight chain hydrocarbon or a branched chain hydrocarbon.
In certain embodiments, the alkyl group has 1 to 12 carbon atoms.
In certain embodiments, the alkyl group has 1 to 6 carbon atoms.
In certain embodiments, R 1 is bromo, trifluoromethyl, t-butyl, cyclohexyl, phenyl, vinyl, vinylphenyl, nonadecylphenyl, N-tolylmethacrylamide, or 1, 10-phenanthroline.
In certain embodiments, R 2 and R 3 are each methyl, ethyl, butyl, dodecyl, phenyl, or phenethyl.
In certain embodiments, step (1) is performed in an aqueous dioxane solution.
In certain embodiments, the volume ratio of dioxane to water is 20-40:1.
In certain embodiments, the inorganic oxide is selenium dioxide.
In certain embodiments, the temperature of the oxidation reaction is 80-120℃and the reaction time is 4-6 hours.
In certain embodiments, step (1) further comprises a first work-up procedure to purify the crude compound ii.
In certain embodiments, the first work-up procedure is specifically to filter the reaction solution, remove the solvent in vacuo, add water and stir until solids appear, then filter, slurry filter in petroleum ether to give compound ii.
In certain embodiments, step (2) is performed in a solvent.
In certain embodiments, the solvent is benzene or toluene.
In certain embodiments, the substitution reaction is carried out under reflux conditions for a reaction time of from 16 to 24 hours.
In certain embodiments, step (2) further comprises a second work-up procedure to purify the crude compound iv.
In certain embodiments, the second post-treatment process comprises removing solvent from the reaction solution in vacuum, purifying by column chromatography, and eluting with petroleum ether/dichloromethane mixed solvent at volume ratio of 2-6:1 to obtain compound IV.
In certain embodiments, step (3) is performed under an inert gas blanket.
In certain embodiments, step (3) is performed in a solvent.
In certain embodiments, the solvent is benzene or toluene.
In certain embodiments, the catalyst is trimethylchlorosilane.
In certain embodiments, the cyclization reaction is carried out under reflux conditions for a reaction time of from 3 to 8 hours.
In certain embodiments, step (3) further comprises a third work-up procedure for purifying the crude compound v or vi.
In certain embodiments, the third post-treatment process is specifically that the reaction solution is subjected to column chromatography purification by removing the solvent in vacuum, and the target compound V or VI is obtained by eluting with a petroleum ether/ethyl acetate mixed solvent with a volume ratio of 2-5:1.
In another aspect, the present invention provides a photochemical buffer synthesized by the above method, where the chemical buffer is one of the following structures:
The beneficial effects of the invention are as follows:
The synthesis method provided by the invention adopts acetophenone derivatives and aniline derivatives as raw materials, and the raw materials are cheap and easy to obtain; the method can design and synthesize photochemical buffering agents with various molecular structures according to the needs, has the advantages of high efficiency and simplicity in synthesis process, simple and convenient post-treatment and low production cost, and is beneficial to the application and popularization of the photochemical long afterglow material.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments.
The synthetic route of the scheme is as follows:
(1) The acetophenone derivative I and inorganic oxide undergo oxidation reaction to obtain a compound II,
(2) The compound II and the aniline derivative III undergo substitution reaction to obtain a compound IV,
(3) ① In the presence of a catalyst, the compound IV and mercaptoethanol react to form a ring to obtain a target compound V,
Or ② in the presence of a catalyst, the compound IV and ethylene glycol undergo a cyclization reaction to obtain a target compound VI,
Wherein,
The inorganic oxide is selenium dioxide;
the catalyst is trimethylchlorosilane;
R 1 is hydrogen, nitro, cyano, hydroxy, acyl, sulfonic, halo, C1-C24 haloalkyl, C3-C10 cycloalkyl, C2-C20 alkenyl, C6-C20 aryl, or C1-C15 heteroaryl with N, O or S, or a combination thereof;
In the present invention, R 1 may also be a C6-C20 aryl or C1-C15 heteroaryl group fused to the phenyl group on the starting acetophenone;
r 2 and R 3 are each independently hydrogen, C1-C24 alkyl, C6-C20 aryl or C1-C15 heteroaryl with N, O or S, or a combination thereof.
In the present invention, unless otherwise indicated, terms used have the ordinary meanings known to those skilled in the art.
The term "nitro" refers to the group-NO 2.
The term "cyano" refers to the group-CN.
The term "hydroxy" refers to the group-OH.
The term "acyl" refers to the group-o=c-R.
The term "sulfonate" refers to the group-SO H.
The term "halogen" or "halo" refers to all halogens, i.e., chlorine, fluorine, bromine or iodine.
The term "haloalkyl" refers to a saturated aliphatic halogenated hydrocarbon group, directly attached, branched or cyclic, having from 1 to 24 carbon atoms, in certain embodiments from 1 to 12, and in certain embodiments from 1 to 6. Haloalkyl includes monohaloalkyl and polyhaloalkyl, and in certain embodiments, haloalkyl is fluoroalkyl or bromoalkyl.
The term "cycloalkyl" refers to a fully saturated or unsaturated non-aromatic ring group having 3 to 10 carbon atoms, and in certain embodiments, cycloalkyl is cyclohexyl.
The term "alkenyl" refers to a straight or branched hydrocarbon having at least one double bond, having 2 to 20 carbon atoms, in certain embodiments the alkenyl group has 2 to 10 carbon atoms, e.g., alkenyl groups including vinyl (-ch=ch 2), 1-propylene (or allyl, -CH 2CH＝CH2), isopropylene (-C (CH 3)＝CH2), etc., alkenyl groups including substituted alkenyl groups or unsubstituted alkenyl groups, substituted alkenyl groups including alkylaryl groups or arylalkenyl groups, in certain embodiments, the substituted alkenyl groups being vinylphenyl groups.
The term "aryl" refers to aromatic carbocyclic groups having single, multiple or multiple condensed (fused) rings, having from 6 to 20 carbon atoms, and having from 1 to 5 rings, especially monocyclic and bicyclic groups. In certain embodiments, the aryl group has 6 to 14 carbon atoms. Aryl includes unsubstituted aryl and substituted aryl, and in certain embodiments, unsubstituted aryl includes phenyl, naphthyl, biphenyl, and the like. "substituted aryl" means that one or more positions in the aryl group are substituted, especially 1-3 substituents, and that the substituents on the substituted aryl group are nitro, cyano, hydroxy, acyl, sulfonic, halogen, alkyl, or combinations thereof, and can be substituted at any position. In certain embodiments, substituted aryl groups include bromophenanthryl, dodecylphenyl, nonadecylphenyl, and the like. Wherein "alkyl" is defined as hereinafter and has the indicated number of carbon atoms.
The term "heteroaryl" refers to an aromatic monocyclic or polycyclic group containing 1 to 4 heteroatoms having 1 to 15 carbon atoms, wherein the heteroatoms are N, O or S. Heteroaryl includes unsubstituted heteroaryl and substituted heteroaryl, the substituents on the substituted heteroaryl being nitro, cyano, hydroxy, acyl, sulfonic, halogen, alkyl, aryl, or combinations thereof.
The term "alkyl" refers to straight or branched chain hydrocarbons having the indicated number of carbon atoms, with the number of carbon atoms in the alkyl groups of the present invention specifically referring to 1-24, in certain embodiments 1-19, and the alkyl groups of the present invention include, but are not limited to, methyl, ethyl, n-butyl, t-butyl, dodecyl, nonadecyl, and the like. In the present invention, alkyl groups also include substituted alkyl groups. "substituted alkyl" means that one or more positions in the alkyl group are substituted, especially 1 to 4 substituents, and may be substituted at any position. For example, "aryl substituted ethyl" refers to an ethyl group in which a hydrogen atom is replaced with one or more aryl groups, and in certain embodiments, the substituted alkyl group is phenethyl.
Furthermore, in the present invention, the selection groups in the definition of the individual substituents listed can be combined with one another to form new substituents which comply with the valence principle, for example N-tolylmethylamide, which is formed by the combination of methylpropenyl, amido and tolyl with one another, is also within the definition of the relevant substituent.
Example 1
4- (2- (4-Bromophenyl) -5, 6-dihydro-1, 4-oxathioladienyl) -N, N-dimethylaniline
(1) 1- (4-Bromophenyl) -2, 2-dihydroxyethanoneIs synthesized by the following steps:
4-bromoacetophenone (20 mmol,1 eq), seO 2 (30 mmol,1.5 eq) was added to the mixture containing dioxane: water=30:1 (20 mL) in a 100mL single-port flask, at 100 ℃ for 5h. Filtering the reaction liquid, removing the solvent in vacuum, adding water, stirring until the solid appears, filtering, pulping and filtering in petroleum ether to obtain the product 1- (4-bromophenyl) -2, 2-dihydroxyethanone.
(2) 1- (4-Bromophenyl) -2- (4- (dimethylamino) phenyl) -2-hydroxyethanoneIs synthesized by the following steps:
1- (4-bromophenyl) -2, 2-dihydroxyethanone (10 mmol,1 eq) and N, N-N-dimethylaniline (10 mmol,1 eq) were added to a 100mL single-necked flask, benzene (15 mL) was further added, and the mixture was refluxed for 18h. The solvent was removed in vacuo and column chromatography (petroleum ether/dichloromethane=4:1) was performed to give the product 1- (4-bromophenyl) -2- (4- (dimethylamino) phenyl) -2-hydroxyethanone.
(3) Synthesis of 4- (2- (4-bromophenyl) -5, 6-dihydro-1, 4-oxathioladienyl) -N, N-dimethylaniline:
1- (4-bromophenyl) -2- (4- (dimethylamino) phenyl) -2-hydroxyethanone (2 mmol), mercaptoethanol (0.5 mL), toluene (5 mL), and trimethylsilyl chloride (0.5 mL) were added to a 25mL three-necked flask and reacted under reflux for 5h. The solvent was removed in vacuo and purified by column chromatography (petroleum ether/ethyl acetate=4:1) to give the title compound in 58% yield.
The structural characterization is as follows:
1H NMR(400MHz,CDCl3)δ7.32-7.23(m,2H),7.14-7.01(m,4H),6.59(d,J＝4.7Hz,2H),4.57-4.40(m,2H),3.26-3.16(m,2H),2.94(s,6H).
Example 2
N, N-dibutyl-4- (2- (4-cyclohexylphenyl) -5, 6-dihydro-1, 4-oxathiolanyi-dine) amine:
(1) 1- (4-cyclohexylphenyl) -2, 2-dihydroxyethanone Is synthesized by the following steps:
4-Cyclohexylacetophenone (20 mmol,1 eq), seO 2 (30 mmol,1.5 eq) were added to the mixture containing dioxane: water=40:1 (20 mL) in a 100mL single-port flask, reaction at 80 ℃ for 6h. Filtering the reaction liquid, removing the solvent in vacuum, adding water, stirring until the solid appears, filtering, pulping and filtering in petroleum ether to obtain the product 1- (4-cyclohexylphenyl) -2, 2-dihydroxyethanone.
(2) 1- (4-Cyclohexylphenyl) -2- (4- (dibutylamino) phenyl) -2-hydroxyethanoneIs synthesized by the following steps:
1- (4-cyclohexylphenyl) -2, 2-dihydroxyethanone (10 mmol,1 eq) and N, N-N-dibutylaniline (10 mmol,1 eq) were added to a 100mL single-necked flask, benzene (15 mL) was added, and the mixture was refluxed for 24h. The solvent was removed in vacuo and column chromatography (petroleum ether/dichloromethane=3:1) gave the product 1- (4-cyclohexylphenyl) -2- (4- (dibutylamino) phenyl) -2-hydroxyethanone.
(3) Synthesis of N, N-dibutyl-4- (2-cyclohexylphenyl-5, 6-dihydro-1, 4-oxathiolanyi-dienyl) aniline:
1- (4-cyclohexylphenyl) -2- (4- (dibutylamino) phenyl) -2-hydroxyethanone (2 mmol), mercaptoethanol (0.5 mL), toluene (5 mL) and trimethylsilyl chloride (0.5 mL) were added to a 25mL three-necked flask under inert gas, and the mixture was refluxed for 8 hours. The solvent was removed in vacuo and purified by column chromatography (petroleum ether/ethyl acetate=3:1) to give the title compound in 50% yield.
The structural characterization is as follows:
1H NMR(400MHz,CDCl3)δ7.13(d,J＝8.3Hz,2H),7.08-7.02(m,2H),6.98(d,J＝8.3Hz,2H),6.47(d,J＝8.9Hz,2H),4.56-4.43(m,2H),3.32-3.15(m,6H),2.42(s,1H),1.82(d,J＝7.3Hz,4H),1.59-1.50(m,6H),1.35(dt,J＝15.2,7.2Hz,8H),0.96(t,J＝7.3Hz,6H).
Example 3
4- (2-4-Cyclohexylphenyl) -5, 6-dihydro-1, 4-oxathiolanyl) -N, N-diphenylethylaniline:
(1) 1- (4-cyclohexylphenyl) -2, 2-dihydroxyethanone Is synthesized by the following steps:
4- (cyclohexyl) acetophenone (20 mmol,1 eq), seO 2 (30 mmol,1.5 eq) were added to the mixture containing dioxane: water=30:1 (20 mL) in a 100mL single-port flask, at 100 ℃ for 4h. Filtering the reaction liquid, removing the solvent in vacuum, adding water, stirring until the solid appears, filtering, pulping and filtering in petroleum ether to obtain the product 1- (4-cyclohexylphenyl) -2, 2-dihydroxyethanone.
(2) 1- (4-Cyclohexylphenyl) -2- (4- (diphenylethylamino) phenyl) -2-hydroxyethanoneIs synthesized by the following steps:
1- (4-cyclohexylphenyl) -2, 2-dihydroxyethanone (10 mmol,1 eq) and N, N-diphenylethylaniline (10 mmol,1 eq) were added to a 100mL single-necked flask, benzene (15 mL) was added, and the mixture was refluxed for 24h. The solvent was removed in vacuo and column chromatography (petroleum ether/dichloromethane=5:1) was performed to give the product 1- (4-cyclohexylphenyl) -2- (4- (diphenylethylamino) phenyl) -2-hydroxyethanone.
(3) Synthesis of 4- (2-4-cyclohexylphenyl) -5, 6-dihydro-1, 4-oxathiolanyl) -N, N-diphenylethylaniline:
1- (4-cyclohexylphenyl) -2- (4- (diphenylethylamino) phenyl) -2-hydroxyethanone (2 mmol), mercaptoethanol (0.5 mL), toluene (5 mL), and trimethylsilicon chloride (0.5 mL) were added to a 25mL three-necked flask, and the mixture was refluxed for 6 hours. The solvent was removed in vacuo and purified by column chromatography (petroleum ether/ethyl acetate=5:1) to give the title compound in 58% yield.
The structural characterization is as follows:
1H NMR(400MHz,CDCl3)δ7.31(m,J＝13.0,5.5Hz,5H),7.26-7.10(m,11H),7.00(d,J＝8.3Hz,2H),6.62(d,J＝8.8Hz,2H),4.60-4.42(m,2H),3.45(dd,J＝15.0,7.0Hz,4H),3.29-3.21(m,2H),2.89-2.73(m,4H),2.42(s,1H),1.87-1.77(m,4H),1.58(s,4H),1.35(d,J＝7.1Hz,2H).
Example 4
4- (2- ([ 1,1' -Biphenyl ] -4-yl) -5, 6-dihydro-1, 4-oxathiolanyl) -N, N-diphenylethylaniline:
(1) 1- ([ 1,1' -biphenyl ] -4-yl) -2, 2-dihydroxyethanone Is synthesized by the following steps:
4-Diacetophenone (20 mmol,1 eq), seO 2 (30 mmol,1.5 eq) was added to the mixture containing dioxane: water=20:1 (20 mL) in a 100mL single-port flask, 110 ℃ for 5h. Filtering the reaction liquid, removing the solvent in vacuum, adding water, stirring until the solid appears, filtering, pulping and filtering in petroleum ether to obtain the product 1- ([ 1,1' -biphenyl ] -4-yl) -2, 2-dihydroxyethanone.
(2) 1- ([ 1,1' -Biphenyl ] -4-yl) -2- (4- (diphenylethylamino) phenyl) -2-hydroxyethanoneIs synthesized by the following steps:
1- ([ 1,1' -biphenyl ] -4-yl) -2, 2-dihydroxyethanone (10 mmol,1 eq) and N, N-diphenylethylaniline (10 mmol,1 eq) were added to a 100mL single-necked flask, benzene (15 mL) was added, and the mixture was refluxed for 20h. The solvent was removed in vacuo and column chromatography (petroleum ether/dichloromethane=6:1) was performed to give the product 1- ([ 1,1' -biphenyl ] -4-yl) -2- (4- (diphenylethylamino) phenyl) -2-hydroxyethanone.
(3) Synthesis of 4- (2- ([ 1,1' -biphenyl ] -4-yl) -5, 6-dihydro-1, 4-oxathiolanyl) -N, N-diphenylethylaniline:
1- ([ 1,1' -biphenyl ] -4-yl) -2- (4- (diphenylethylamino) phenyl) -2-hydroxy ethanone (2 mmol), mercaptoethanol (0.5 mL), toluene (5 mL), and trimethylsilicon chloride (0.5 mL) were added to a 25mL three-necked flask under inert gas, and the mixture was refluxed for 5 hours. The solvent was removed in vacuo and purified by column chromatography (petroleum ether/ethyl acetate=4:1) to give the title compound in 58% yield.
The structural characterization is as follows:
1H NMR(400MHz,CDCl3)δ7.58(t,J＝8.5Hz,2H),7.42(td,J＝12.0,9.1Hz,4H),7.37-7.27(m,8H),7.21(dd,J＝17.8,10.5Hz,8H),6.66(t,J＝9.3Hz,2H),4.57(s,2H),3.68-3.38(m,4H),3.29(s,2H),2.84(d,J＝5.9Hz,4H).
Example 5
N, N-diphenyl-4- (2- (4 '-vinyl- [1,1' -biphenyl ] -4-yl) -5, 6-dihydro-1, 4-oxathiolanyi dienyl) aniline:
(1) 1- (4 '-vinyl- [1,1' -biphenyl ] -4-yl) -2, 2-dihydroxyethanone Is synthesized by the following steps:
4-Vinyldiacetone (20 mmol,1 eq), seO 2 (30 mmol,1.5 eq) were added to a mixture containing dioxane: water=30:1 (20 mL) in a 100mL single-port flask, at 100 ℃ for 5h. Filtering the reaction liquid, removing the solvent in vacuum, adding water, stirring until the solid appears, filtering, pulping and filtering in petroleum ether to obtain the product 1- (4 '-vinyl- [1,1' -biphenyl ] -4-yl) -2, 2-dihydroxyethanone.
(2) 2- (4- (Diphenylamino) phenyl) -2-hydroxy-1- (4 '-vinyl- [1,1' -biphenyl ] -4-yl) ethanoneIs synthesized by the following steps:
1- (4 '-vinyl- [1,1' -biphenyl ] -4-yl) -2, 2-dihydroxyethanone (10 mmol,1 eq) and N, N-diphenylaniline (10 mmol,1 eq) were added to a 100mL single-necked flask, benzene (5 mL) was added, and the mixture was refluxed for 20h. The solvent was removed in vacuo and column chromatography (petroleum ether/dichloromethane=4:1) was performed to give the product 2- (4- (diphenylamino) phenyl) -2-hydroxy-1- (4 '-vinyl- [1,1' -biphenyl ] -4-yl) ethanone.
(3) Synthesis of N, N-diphenyl-4- (2- (4 '-vinyl- [1,1' -biphenyl ] -4-yl) -5, 6-dihydro-1, 4-oxathiadienyl) aniline:
2- (4- (Diphenylamino) phenyl) -2-hydroxy-1- (4 '-vinyl- [1,1' -biphenyl ] -4-yl) ethanone (2 mmol), mercaptoethanol (0.5 mL), toluene (5 mL) and trimethylsilicon chloride (0.5 mL) were added to a 25mL three-necked flask under inert gas, and the mixture was refluxed for 6 hours. The solvent was removed in vacuo and purified by column chromatography (petroleum ether/ethyl acetate=4:1) to give the title compound in 61% yield.
The structural characterization is as follows:
1H NMR(400MHz,CDCl3)δ7.55(d,J＝8.4Hz,2H),7.49(d,J＝8.2Hz,2H),7.42(d,J＝8.6Hz,2H),7.28-7.22(m,6H),7.14(d,J＝8.8Hz,2H),7.12-7.07(m,4H),7.02(t,J＝7.3Hz,2H),6.92(d,J＝8.6Hz,2H),6.77(dd,J＝17.6,10.9Hz,1H),5.81(dd,J＝17.6,0.8Hz,1H),5.49-5.18(m,1H),4.62-4.49(m,2H),3.32-3.11(m,2H).
Example 6
N, N-diphenyl-4- (2-vinylphenyl-5, 6-dihydro-1, 4-oxathiolenyl) aniline:
the synthesis method is the same as that of example 5, 4-vinyl acetophenone is used for replacing 4-vinyl biacetophenone in example 5, and the target compound is obtained, and the product yield of the third step is 58%.
The structural characterization is as follows:
1H NMR(400MHz,CDCl3)δ7.33-7.22(m,8H),7.20-7.11(m,6H),7.06(dd,J＝10.5,4.2Hz,2H),7.00-6.94(m,2H),6.80-6.64(m,1H),5.78(dd,J＝17.6,0.8Hz,1H),5.33-5.22(m,1H),4.59-4.46(m,2H),3.31-3.19(m,2H).
Example 7
4- (2- (4 '-Nonadecyl- [1,1' -biphenyl ] -4-yl) -5, 6-dihydro-1, 4-oxathiolanyl) -N, N-diphenylaniline:
The synthesis method is the same as that of example 5, 4-nonadecyl diacetone is used for replacing 4-vinyl diacetone in example 5, and the target compound is obtained, and the product yield of the third step is 56%.
The structural characterization is as follows:
1H NMR(400MHz,CDCl3)δ7.50(d,J＝8.1Hz,2H),7.41(d,J＝8.4Hz,2H),7.27-7.24(m,6H),7.16-7.07(m,8H),7.02(t,J＝7.3Hz,2H),6.93(dd,J＝8.8,2.1Hz,2H),4.58-4.54(m,2H),3.30-3.25(m,2H),2.72-2.58(m,2H),1.68-1.62(m,2H),1.28(s,32H),0.91(t,J＝6.8Hz,3H).
Example 8
4- (2- ([ 1,1' -Biphenyl ] -4-yl) -5, 6-dihydro-1, 4-oxathioladienyl) -N, N-behenyl-aniline:
The synthesis method was the same as that of example 4, and N, N-dodecylaniline was used in place of N, N-diphenylethylaniline in example 4 to obtain the objective compound, and the product yield in the third step was 57%.
The structural characterization is as follows:
1H NMR(400MHz,CDCl3)δ7.57(dt,J＝3.1,1.9Hz,2H),7.45-7.38(m,4H),7.35-7.31(m,1H),7.31-7.29(m,2H),7.14-7.06(m,2H),6.50(t,J＝5.9Hz,2H),4.58-4.49(m,2H),3.31-3.16(m,6H),1.57(d,J＝5.6Hz,4H),1.30(d,J＝10.4Hz,36H),0.91(t,J＝6.9Hz,6H).
Example 9
4- (2-4- (1, 10-Phenanthroline-5-yl) phenyl-5, 6-dihydro-1, 4-oxathiadienyl) -N, N-dimethylaniline:
The synthesis method is the same as that of example 1, 4- (1, 10-phenanthroline) acetophenone is used for replacing 4-bromoacetophenone in example 1, and the target compound is obtained, and the product yield of the third step is 52%.
The structural characterization is as follows:
1H NMR(400MHz,CDCl3)δ9.19(d,J＝4.2Hz,2H),8.33-8.14(m,2H),7.70(s,1H),7.63(dt,J＝18.4,9.2Hz,1H),7.58-7.47(m,1H),7.44-7.33(m,2H),7.33-7.27(m,2H),7.16(dd,J＝22.4,8.8Hz,2H),6.64(d,J＝8.7Hz,2H),4.71-4.45(m,2H),3.36-3.19(m,2H),2.95(s,6H).
example 10
4- (2- ([ 1,1' -Biphenyl ] -4-yl) -5, 6-dihydro-1, 4-oxathiolanyl) -N, N-dimethylaniline:
The synthesis method is the same as that of example 1, 4-bromoacetophenone in example 1 is replaced by 4-biacetophenone, and the target compound is obtained, and the product yield in the third step is 49%.
The structural characterization is as follows:
1H NMR(400MHz,CDCl3)δ7.56(d,J＝7.6Hz,2H),7.52-7.35(m,4H),7.34-7.30(m,1H),7.28(s,2H),7.13(t,J＝15.9Hz,2H),6.60(d,J＝8.5Hz,2H),4.61-4.46(m,2H),3.33-3.19(m,2H),3.07-2.76(m,6H).
Example 11
4- (2- (4-Tert-butyl) phenyl) -5, 6-dihydro-1, 4-oxathiolanyl) -N, N-dimethylaniline:
The synthesis method is the same as that of example 1, 4-tert-butyl acetophenone is used for replacing 4-bromoacetophenone in example 1, and the target compound is obtained, and the product yield of the third step is 62%.
The structural characterization is as follows:
1H NMR(400MHz,CDCl3)δ7.22-7.08(m,6H),6.60(d,J＝8.8Hz,2H),4.58-4.43(m,2H),3.28-3.17(m,2H),2.94(s,6H),1.26(s,9H).
Example 12
4- (2- (4-Tert-butyl) phenyl) -5, 6-dihydro-1, 4-oxathiadienyl) -N, N-dodecylaniline:
the synthesis method was the same as that of example 11, and N, N-N-dodecylaniline was used in place of N, N-N-methylaniline in example 11 to obtain the objective compound, and the product yield in the third step was 53%.
The structural characterization is as follows:
1H NMR(400MHz,CDCl3)δ7.28(s,1H),7.19-7.12(m,8H),7.24-6.93(m,12H),7.10-7.05(m,4H),6.48(d,J＝8.9Hz,4H),6.48(d,J＝8.9Hz,4H),4.50(dd,J＝5.1,3.8Hz,4H),4.50(dd,J＝5.1,3.8Hz,4H),3.28-3.15(m,12H),3.31-3.16(m,12H),1.57(s,9H),1.57(s,8H),1.45-1.30(m,23H),1.35-1.27(m,71H),1.30(s,16H),1.28(d,J＝7.7Hz,85H),0.91(t,J＝6.9Hz,12H),0.91(t,J＝6.9Hz,12H),0.06-0.05(m,2H).
Example 13
N, N-dimethyl-4- (2- (4-vinyl phenyl) -5, 6-dihydro-1, 4-oxathiolenyl) aniline:
The synthesis method is the same as that of example 1, 4-vinyl acetophenone is used for replacing 4-bromoacetophenone in example 1, and the target compound is obtained, and the product yield of the third step is 54%.
The structural characterization is as follows:
1H NMR(400MHz,CDCl3)δ7.22-7.08(m,6H),6.59(d,J＝8.6Hz,2H),5.69(d,J＝17.6Hz,1H),5.20(d,J＝10.9Hz,1H),4.55-4.47(m,2H),3.27-3.20(m,2H),2.94(s,6H).
Example 14
N, N-dimethyl-4- (2- (4-nitrophenyl) -5, 6-dihydro-1, 4-oxathioladienyl) aniline:
the synthesis method is the same as that of example 1, 4-nitroacetophenone is used for replacing 4-bromoacetophenone in example 1, and the target compound is obtained, and the product yield of the third step is 50%.
Example 15
4- (3- (4- (Dimethylamino) phenyl) -5, 6-dihydro-1, 4-oxathiolan-2-yl) benzonitrile:
the synthesis method is the same as that of example 1, 4-cyanoacetophenone is used for replacing 4-bromoacetophenone in example 1, and the target compound is obtained, and the product yield of the third step is 62%.
Example 16
N, N-dimethyl-4- (2-naphthyl) -5, 6-dihydro-1, 4-oxathiadienyl) aniline:
The synthesis method is the same as that of example 1, 4-naphthyl ethanone is used for replacing 4-bromoacetophenone in example 1, and the target compound is obtained, and the product yield of the third step is 58%.
Example 17
N, N-dimethyl-4- (2- (4-trifluoromethyl) phenyl) -5, 6-dihydro-1, 4-oxathiolanyi-dine:
the synthesis method is the same as that of example 1, 4-trifluoromethyl acetophenone is used for replacing 4-bromoacetophenone in example 1, and the target compound is obtained, and the product yield of the third step is 47%.
Example 18
N- ((4 '- (3- (4- (diphenylamino) phenyl) -5, 6-dihydro-1, 4-oxathiolan-2-yl) - [1,1' -biphenyl ] -4-yl) methyl) methacrylamide:
The synthesis method is the same as that of example 5, N- ((4 '-acetyl- [1,1' -biphenyl ] -4-yl) methyl) methacrylamide is used for replacing 4-vinyl biacetophenone in example 5, and the target compound is obtained, and the product yield of the third step is 52%.
Example 19
4- (3-Phenyl-5, 6-dihydro-1, 4-dioxin-2-yl) aniline:
(1) 2, 2-dihydroxyacetophenone Is synthesized by the following steps:
Acetophenone (20 mmol,1 eq), seO 2 (30 mmol,1.5 eq) was added to the mixture containing dioxane: water=30:1 (20 mL) in a 100mL single-port flask, at 100 ℃ for 5h. Filtering the reaction liquid, removing the solvent in vacuum, adding water, stirring until the solid appears, filtering, pulping and filtering in petroleum ether to obtain the product 2, 2-dihydroxyacetophenone.
(2) 2- (4-Aminophenyl) -2-hydroxy-1-acetophenoneIs synthesized by the following steps:
2, 2-dihydroxyacetophenone (10 mmol,1 eq) and aniline (10 mmol,1 eq) were added to a 100mL single-necked flask, benzene (15 mL) was added, and the mixture was refluxed for 18h. The solvent was removed in vacuo and purified by column chromatography (petroleum ether/dichloromethane=4:1) to give the product 2- (4-aminophenyl) -2-hydroxy-1-acetophenone.
(3) Synthesis of 4- (3-phenyl-5, 6-dihydro-1, 4-dioxin-2-yl) aniline:
2- (4-aminophenyl) -2-hydroxy-1-acetophenone (2 mmol), ethylene glycol (0.5 mL), toluene (5 mL), and trimethylsilyl chloride (0.5 mL) were added to a 25mL three-necked flask, and the mixture was refluxed for 6 hours. The solvent was removed in vacuo and purified by column chromatography (petroleum ether/ethyl acetate=4:1) to give the title compound in 58% yield.
The structural characterization is as follows:
1H NMR(400MHz,CDCl3)δ7.32-7.23(m,2H),7.14-7.01(m,5H),6.59(d,J＝4.7Hz,2H),4.57-4.40(m,2H),3.26-3.16(m,2H).
Example 20
4- (3- (4-Fluorophenyl) -5, 6-dihydro-1, 4-dioxin-2-yl) -N, N-dimethylaniline:
(1) 1- (4-fluorophenyl) -2, 2-dihydroxyethanone Is synthesized by the following steps:
4-fluoro acetophenone (20 mmol,1 eq), seO 2 (30 mmol,1.5 eq) was added to the mixture containing dioxane: water=30:1 (20 mL) in a 100mL single-port flask, at 100 ℃ for 5h. Filtering the reaction liquid, removing the solvent in vacuum, adding water, stirring until the solid appears, filtering, pulping and filtering in petroleum ether to obtain the product 1- (4-fluorophenyl) -2, 2-dihydroxyethanone.
(2) 1- (4-Fluorophenyl) -2- (4- (dimethylamino) phenyl) -2-hydroxyethyl ketoneIs synthesized by the following steps:
1- (4-fluorophenyl) -2, 2-dihydroxyethanone (10 mmol,1 eq) and N, N-dimethylaniline (10 mmol,1 eq) were added to a 100mL single-necked flask, benzene (15 mL) was added, and the mixture was refluxed for 18h. The solvent was removed in vacuo and column chromatography (petroleum ether/dichloromethane=4:1) was performed to give the product 1- (4-fluorophenyl) -2- (4- (dimethylamino) phenyl) -2-hydroxyethyl ketone.
(3) Synthesis of 4- (3- (4-fluorophenyl) -5, 6-dihydro-1, 4-dioxin-2-yl) -N, N-dimethylaniline:
1- (4-fluorophenyl) -2- (4- (dimethylamino) phenyl) -2-hydroxyethanone (2 mmol), ethylene glycol (0.5 mL), toluene (5 mL), and trimethylsilyl chloride (0.5 mL) were added to a 25mL three-necked flask under inert gas, and the mixture was refluxed for 8 hours. The solvent was removed in vacuo and purified by column chromatography (petroleum ether/ethyl acetate=4:1) to give the title compound in 58% yield.
The structural characterization is as follows:
1H NMR(400MHz,CDCl3)δ7.32-7.23(m,2H),7.14-7.08(m,4H),6.51(d,J＝4.7Hz,2H),4.57-4.40(d,2H),3.26-3.13(d,2H),2.95(s,6H).
Example 21
N, N-dibutyl-4- (3- (4- (trifluoromethyl) phenyl) -5, 6-dihydro-1, 4-dioxin-2-yl) aniline:
(1) 1- (4-trifluoromethylphenyl) -2, 2-dihydroxyethanone Is synthesized by the following steps:
4-trifluoromethyl acetophenone (20 mmol,1 eq), seO 2 (30 mmol,1.5 eq) was added to a mixture containing dioxane: water=40:1 (20 mL) in a 100mL single-port flask, reaction was carried out at 90 ℃ for 6h. Filtering the reaction liquid, removing the solvent in vacuum, adding water, stirring until the solid appears, filtering, pulping and filtering in petroleum ether to obtain the product 1- (4-trifluoromethyl phenyl) -2, 2-dihydroxyethanone.
(2) 1- (4-Trifluoromethylphenyl) -2- (4- (dibutylamino) phenyl) -2-hydroxyethanoneIs synthesized by the following steps: /(I)
1- (4-Trifluoromethylphenyl) -2, 2-dihydroxyethanone (10 mmol,1 eq) and N, N-N-dibutylaniline (10 mmol,1 eq) were added to a 100mL single-necked flask, benzene (15 mL) was added, and the mixture was refluxed for 20 hours. The solvent was removed in vacuo and column chromatography (petroleum ether/dichloromethane=4:1) was performed to give the product 1- (4-trifluoromethylphenyl) -2- (4- (dibutylamino) phenyl) -2-hydroxyethanone.
(3) Synthesis of N, N-dibutyl-4- (3- (4- (trifluoromethyl) phenyl) -5, 6-dihydro-1, 4-dioxin-2-yl) aniline:
1- (4-trifluoromethylphenyl) -2- (4- (dibutylamino) phenyl) -2-hydroxyethanone (2 mmol), ethylene glycol (0.5 mL), toluene (5 mL) and trimethylsilyl chloride (0.5 mL) were added to a 25mL three-necked flask under inert gas, and the mixture was refluxed for 6 hours. The solvent was removed in vacuo and purified by column chromatography (petroleum ether/ethyl acetate=4:1) to give the title compound in 59% yield.
The structural characterization is as follows:
1H NMR(400MHz,CDCl3)δ7.13(d,J＝8.3Hz,2H),7.08-7.02(m,2H),6.98(d,J＝8.3Hz,2H),6.47(d,J＝8.9Hz,2H),4.56-4.43(m,2H),3.32-3.15(m,2H),1.82(d,J＝7.3Hz,4H),1.35(dt,J＝15.2,7.2Hz,8H),0.96(t,J＝7.3Hz,6H).
example 22
4- (3- (4- (5-Bromophenanthr-3-yl) phenyl) -5, 6-dihydro-1, 4-dioxin-2-yl) -N, N-dimethylaniline:
The synthesis method was the same as that of example 20, and 4- (5-bromophenanthr-3-yl) acetophenone was used instead of 4-fluoroacetophenone in example 20 to obtain the target compound, and the product yield in the third step was 54%.
Example 23
4- (3- ([ 1,1' -Biphenyl ] -4-yl) -5, 6-dihydro-1, 4-dioxin-2-yl) -N, N-diphenylaniline:
The synthesis method is the same as that of example 20, the target compound is obtained by replacing 4-fluoro acetophenone in example 20 with biacetophenone and replacing N, N-dimethylaniline in example 20 with N, N-dimethylaniline in example 20, and the product yield in the third step is 56%.
To sum up: the synthesis method provided by the invention adopts acetophenone derivatives and aniline derivatives as raw materials, the raw materials are cheap and easy to obtain, photochemical buffering agents with various molecular structures can be designed and synthesized according to the needs, the synthesis process is efficient and simple, the post-treatment is simple and convenient, the production cost is low, and the application and popularization of the photochemical long afterglow material are facilitated.
The above description is only of a preferred form of the invention, it being noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the inventive concept, which shall also be regarded as being within the scope of the invention.
Claims (9)
1. The synthesis method of the photochemical caching agent is characterized by comprising the following steps of:
(1) The acetophenone derivative I and inorganic oxide undergo oxidation reaction to obtain a compound II,
Ⅰ Ⅱ
(2) The compound II and the aniline derivative III undergo substitution reaction to obtain a compound IV,
Ⅱ Ⅲ Ⅳ
(3) ① In the presence of a catalyst, the compound IV and mercaptoethanol react to form a ring to obtain a target compound V,
Ⅳ Ⅴ
Or (b)
② In the presence of a catalyst, the compound IV and glycol undergo a cyclization reaction to obtain a target compound VI,
Ⅳ Ⅵ
Wherein,
R 1 is hydrogen, nitro, cyano, halogen, tert-butyl, C1-C12 haloalkyl, C3-C10 cycloalkyl, C2-C10 alkenyl, C1-C20 alkylbenzene, vinylphenyl, N-tolylmethacrylamide or 1, 10-phenanthroline;
R 2 and R 3 are each independently hydrogen, C1-C12 alkyl, phenyl or phenethyl;
The inorganic oxide is selenium dioxide;
the catalyst is trimethylchlorosilane.
2. The synthesis method according to claim 1, wherein,
The halogen is chlorine, fluorine, bromine or iodine;
The haloalkyl is fluoroalkyl or bromoalkyl.
3. The synthesis method according to claim 1, wherein,
R 1 is bromo, trifluoromethyl, t-butyl, cyclohexyl, phenyl, vinyl, vinylphenyl, nonadecylphenyl, N-tolylmethacrylamide or 1, 10-phenanthroline;
R 2 and R 3 are each methyl, ethyl, butyl, dodecyl, phenyl or phenethyl.
4. The synthesis method according to claim 1, wherein,
The step (1) is carried out in an aqueous dioxane solution;
The volume ratio of dioxane to water is 20-40:1;
The temperature of the oxidation reaction is 80-120 o C, and the reaction time is 4-6 h.
5. The synthesis method according to claim 1, wherein,
The step (1) further comprises a first post-treatment process for purifying the crude compound II;
The first post-treatment process specifically comprises the steps of filtering reaction liquid, removing solvent in vacuum, adding water, stirring until solids appear, filtering, pulping in petroleum ether, and filtering to obtain a compound II.
6. The synthesis method according to claim 1, wherein,
Said step (2) is carried out in a solvent;
The solvent is benzene or toluene;
the substitution reaction is carried out under reflux conditions for a reaction time of 16-24 h.
7. The synthesis method according to claim 1, wherein,
The step (2) also comprises a second post-treatment process for purifying the crude product of the compound IV;
The second post-treatment process comprises the steps of removing the solvent from the reaction liquid in vacuum, purifying by column chromatography, and eluting by using a petroleum ether/dichloromethane mixed solvent with the volume ratio of 2-6:1 to obtain the compound IV.
8. The synthesis method according to claim 1, wherein,
The step (3) is carried out under the protection of inert gas;
Said step (3) is carried out in a solvent;
The solvent is benzene or toluene;
the cyclization reaction is carried out under reflux conditions, and the reaction time is 3-8 h.
9. The synthesis method according to claim 1, wherein,
The step (3) further comprises a third post-treatment process for purifying the crude compound V or VI;
the third post-treatment process comprises the steps of removing the solvent from the reaction liquid in vacuum, performing column chromatography purification, and eluting with a petroleum ether/ethyl acetate mixed solvent with the volume ratio of 2-5:1 to obtain the target compound V or VI.
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