CN114874279A - Steroid-perylene diimide compound, preparation method and preparation and application of fluorescent film thereof - Google Patents
Steroid-perylene diimide compound, preparation method and preparation and application of fluorescent film thereof Download PDFInfo
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- CN114874279A CN114874279A CN202210670747.2A CN202210670747A CN114874279A CN 114874279 A CN114874279 A CN 114874279A CN 202210670747 A CN202210670747 A CN 202210670747A CN 114874279 A CN114874279 A CN 114874279A
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- steroid
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- perylene diimide
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- 238000002360 preparation method Methods 0.000 title claims description 17
- LGJMUZUPVCAVPU-UHFFFAOYSA-N beta-Sitostanol Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(C)CCC(CC)C(C)C)C1(C)CC2 LGJMUZUPVCAVPU-UHFFFAOYSA-N 0.000 claims abstract description 27
- OILXMJHPFNGGTO-UHFFFAOYSA-N (22E)-(24xi)-24-methylcholesta-5,22-dien-3beta-ol Chemical group C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)C=CC(C)C(C)C)C1(C)CC2 OILXMJHPFNGGTO-UHFFFAOYSA-N 0.000 claims abstract description 18
- OQMZNAMGEHIHNN-UHFFFAOYSA-N 7-Dehydrostigmasterol Chemical group C1C(O)CCC2(C)C(CCC3(C(C(C)C=CC(CC)C(C)C)CCC33)C)C3=CC=C21 OQMZNAMGEHIHNN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229940076810 beta sitosterol Drugs 0.000 claims abstract description 18
- NJKOMDUNNDKEAI-UHFFFAOYSA-N beta-sitosterol Natural products CCC(CCC(C)C1CCC2(C)C3CC=C4CC(O)CCC4C3CCC12C)C(C)C NJKOMDUNNDKEAI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229940079593 drug Drugs 0.000 claims abstract description 18
- 239000003814 drug Substances 0.000 claims abstract description 18
- KZJWDPNRJALLNS-VJSFXXLFSA-N sitosterol Chemical group C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CC[C@@H](CC)C(C)C)[C@@]1(C)CC2 KZJWDPNRJALLNS-VJSFXXLFSA-N 0.000 claims abstract description 18
- 229950005143 sitosterol Drugs 0.000 claims abstract description 18
- 239000011521 glass Substances 0.000 claims abstract description 14
- RQOCXCFLRBRBCS-UHFFFAOYSA-N (22E)-cholesta-5,7,22-trien-3beta-ol Chemical group C1C(O)CCC2(C)C(CCC3(C(C(C)C=CCC(C)C)CCC33)C)C3=CC=C21 RQOCXCFLRBRBCS-UHFFFAOYSA-N 0.000 claims abstract description 9
- DNVPQKQSNYMLRS-NXVQYWJNSA-N Ergosterol Chemical group CC(C)[C@@H](C)C=C[C@H](C)[C@H]1CC[C@H]2C3=CC=C4C[C@@H](O)CC[C@]4(C)[C@@H]3CC[C@]12C DNVPQKQSNYMLRS-NXVQYWJNSA-N 0.000 claims abstract description 9
- HZYXFRGVBOPPNZ-UHFFFAOYSA-N UNPD88870 Chemical group C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)=CCC(CC)C(C)C)C1(C)CC2 HZYXFRGVBOPPNZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000016831 stigmasterol Nutrition 0.000 claims abstract description 9
- BFDNMXAIBMJLBB-UHFFFAOYSA-N stigmasterol Chemical group CCC(C=CC(C)C1CCCC2C3CC=C4CC(O)CCC4(C)C3CCC12C)C(C)C BFDNMXAIBMJLBB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229940032091 stigmasterol Drugs 0.000 claims abstract description 9
- QYIXCDOBOSTCEI-QCYZZNICSA-N (5alpha)-cholestan-3beta-ol Chemical group C([C@@H]1CC2)[C@@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@H](C)CCCC(C)C)[C@@]2(C)CC1 QYIXCDOBOSTCEI-QCYZZNICSA-N 0.000 claims abstract description 8
- QYIXCDOBOSTCEI-UHFFFAOYSA-N alpha-cholestanol Chemical group C1CC2CC(O)CCC2(C)C2C1C1CCC(C(C)CCCC(C)C)C1(C)CC2 QYIXCDOBOSTCEI-UHFFFAOYSA-N 0.000 claims abstract description 8
- DNVPQKQSNYMLRS-SOWFXMKYSA-N ergosterol Chemical group C1[C@@H](O)CC[C@]2(C)[C@H](CC[C@]3([C@H]([C@H](C)/C=C/[C@@H](C)C(C)C)CC[C@H]33)C)C3=CC=C21 DNVPQKQSNYMLRS-SOWFXMKYSA-N 0.000 claims abstract description 3
- HCXVJBMSMIARIN-UHFFFAOYSA-N stigmasterol Chemical group C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)C=CC(CC)C(C)C)C1(C)CC2 HCXVJBMSMIARIN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 91
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 87
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 50
- 239000007787 solid Substances 0.000 claims description 39
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- 229960001701 chloroform Drugs 0.000 claims description 17
- 238000010992 reflux Methods 0.000 claims description 16
- 238000000967 suction filtration Methods 0.000 claims description 16
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000012074 organic phase Substances 0.000 claims description 14
- 239000003208 petroleum Substances 0.000 claims description 14
- 239000003480 eluent Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000004440 column chromatography Methods 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 7
- 238000007865 diluting Methods 0.000 claims description 7
- 239000012452 mother liquor Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229930182558 Sterol Natural products 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- -1 sterol chloroformate Chemical class 0.000 claims description 6
- 235000003702 sterols Nutrition 0.000 claims description 6
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims description 6
- KWTSXDURSIMDCE-QMMMGPOBSA-N (S)-amphetamine Chemical compound C[C@H](N)CC1=CC=CC=C1 KWTSXDURSIMDCE-QMMMGPOBSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229940025084 amphetamine Drugs 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 229940125904 compound 1 Drugs 0.000 claims description 4
- 229940126214 compound 3 Drugs 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 229940125782 compound 2 Drugs 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 150000003432 sterols Chemical class 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims 1
- LYUQWQRTDLVQGA-UHFFFAOYSA-N 3-phenylpropylamine Chemical compound NCCCC1=CC=CC=C1 LYUQWQRTDLVQGA-UHFFFAOYSA-N 0.000 abstract description 9
- 238000011896 sensitive detection Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 40
- 239000010408 film Substances 0.000 description 29
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 22
- 239000000203 mixture Substances 0.000 description 15
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 15
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 15
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 10
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 10
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 8
- 239000000725 suspension Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- DNVPQKQSNYMLRS-APGDWVJJSA-N ergosterol Chemical compound C1[C@@H](O)CC[C@]2(C)[C@@H](CC[C@@]3([C@@H]([C@H](C)/C=C/[C@H](C)C(C)C)CC[C@H]33)C)C3=CC=C21 DNVPQKQSNYMLRS-APGDWVJJSA-N 0.000 description 6
- 239000007850 fluorescent dye Substances 0.000 description 6
- HCXVJBMSMIARIN-PHZDYDNGSA-N stigmasterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)/C=C/[C@@H](CC)C(C)C)[C@@]1(C)CC2 HCXVJBMSMIARIN-PHZDYDNGSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000005316 response function Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000004081 narcotic agent Substances 0.000 description 3
- KJOLVZJFMDVPGB-UHFFFAOYSA-N perylenediimide Chemical compound C=12C3=CC=C(C(NC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)NC(=O)C4=CC=C3C1=C42 KJOLVZJFMDVPGB-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 229920001109 fluorescent polymer Polymers 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229960001252 methamphetamine Drugs 0.000 description 2
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011540 sensing material Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 150000003431 steroids Chemical class 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- LQGKDMHENBFVRC-UHFFFAOYSA-N 5-aminopentan-1-ol Chemical compound NCCCCCO LQGKDMHENBFVRC-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000007877 drug screening Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000001906 matrix-assisted laser desorption--ionisation mass spectrometry Methods 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 230000003533 narcotic effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J43/00—Normal steroids having a nitrogen-containing hetero ring spiro-condensed or not condensed with the cyclopenta(a)hydrophenanthrene skeleton
- C07J43/003—Normal steroids having a nitrogen-containing hetero ring spiro-condensed or not condensed with the cyclopenta(a)hydrophenanthrene skeleton not condensed
-
- 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
-
- 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"
-
- 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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- 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
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Biochemistry (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Steroid Compounds (AREA)
Abstract
The invention discloses a steroid-perylene diimide compound, which has the following structure, wherein m is 7-11; n is 2-5; r is selected from beta-sitosterol, stigmasterol, ergosterol or dihydrocholesterol. According to the invention, the steroid-perylene diimide compound is attached to the inner layer of the glass tube to prepare the fluorescent film, so that the fluorescent film can quickly respond to the phenylpropylamine drugs, and the quick and sensitive detection of the vapor of the phenylpropylamine drugs is realized.
Description
Technical Field
The invention relates to a fluorescent compound, in particular to a steroid-perylene diimide compound, a preparation method and preparation and application of a fluorescent film thereof.
Background
The high performance liquid chromatography is one of common methods for detecting the ice toxicity, has the characteristics of high separation efficiency, high analysis speed, low requirement on the stability of a sample and the like, but has the advantages of large pretreatment workload, strong professional property, expensive detection and high requirement on the sensitivity of instrument consumables, so that the high performance liquid chromatography is not suitable for relevant departments of the basic level.
In addition, the fluorescent sensing material is also a popular research direction in recent years, but no matter the side chain carries the amino fluorescent polymer molecule or the heteroatom-containing fluorescent polymer realizes the detection of the methamphetamine gas which is a product obtained after the glacial toxic alkalization treatment, the fluorescent sensing material has certain defects, such as large background interference, short service life, reagent pollution, harsh and toxic preparation conditions and the like. These limitations are also a problem to be solved in this patent.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a fluorescent compound with a sensing function on the p-propylamine narcotic drug and a sensing film, wherein the film has the characteristics of high sensitivity, strong affinity and the like on the narcotic drug, has the synthesis characteristics of simple preparation, high stability and the like, and can realize the rapid and sensitive detection on the steam of the p-propylamine narcotic drug.
The technical scheme is as follows: the steroid-perylene diimide compound provided by the invention has the following structure:
wherein m is 7-11; n is 2-5; r is selected from beta-sitosterol, stigmasterol, ergosterol or dihydrocholesterol.
The preparation method of the steroid-perylene diimide compound comprises the following steps:
(1) adding anhydrous sodium carbonate into a reaction container, then adding an anhydrous tetrahydrofuran solution of sterol, stirring, dropwise adding an anhydrous tetrahydrofuran solution of triphosgene after ice bath, stirring and reacting for 1-3 hours in ice bath after dropwise adding is finished, and then stirring and reacting for 10-20 hours at room temperature; diluting the reactant with hexane after the reaction is finished, carrying out suction filtration, taking filtrate, carrying out reduced pressure concentration, and separating a crude product by using a chromatographic column to prepare a light yellow oily compound 1, namely sterol chloroformate;
(2) dissolving alkyl alcohol amine in trichloromethane, stirring at room temperature until the solution is uniform and transparent, slowly dropwise adding trichloromethane solution of sterol chloroformate in ice bath, and continuously stirring at room temperature after dropwise adding, and reacting for 10-20 hours; after the reaction is finished, washing with a dilute acid solution, then washing with water, separating an organic phase, and washing with petroleum ether to prepare a white solid compound 2;
(3) suspending 3, 4, 9, 10-perylenetetracarboxylic dianhydride and amino alkanoic acid in N-methylpyrrolidone, and carrying out reflux reaction at 100 ℃ and 130 ℃ for 8-12 hours; after the reaction is finished, cooling to room temperature, pouring into a sodium hydroxide dilute solution, stirring for 0.2-1.0 hour, then carrying out suction filtration, washing filter residues for 0.2-1.0 hour by using acetic acid, carrying out suction filtration, washing the filter residues by using an acetic acid solution, and preparing a dark red solid compound 3;
(4) dissolving the compound 3 in thionyl chloride, refluxing for 5 hours at 80-110 ℃, removing the dimethylsulfoxide by rotary evaporation, and drying in vacuum to obtain a black red solid, namely a compound 4;
(5) dissolving the compound 4 and the compound 1 in dichloromethane, adding anhydrous potassium carbonate, carrying out reflux reaction at 55 ℃ for 8-12 hours, filtering after the reaction is finished, removing an organic phase from filtrate, and carrying out column chromatography separation on obtained solids by using an eluent to prepare a red solid target compound.
In the preparation method of the steroid-perylene diimide compound, the chromatographic column in the step (1) is a petroleum ether/dichloromethane chromatographic column.
In the preparation method of the steroid-perylene diimide compound, the eluent in the step (5) is a mixed solvent of dichloromethane and acetone.
According to the preparation method of the steroid-perylene diimide compound, in the step (5), the volume ratio of the eluent dichloromethane to acetone is 20: 1-10: 1.
The preparation method of the steroid-perylene diimide compound comprises the steps (1) to (5) under the protection of nitrogen.
The fluorescent film is prepared by dissolving and diluting the steroid-perylene diimide compound by an organic solution, adding the solution into a transparent container, and volatilizing the solvent.
The fluorescent film is prepared by the following steps:
(1) dissolving the steroid-perylene diimide compound solid of claim 1 in tetrahydrofuran to prepare a mother solution;
(2) diluting the mother liquor by one time with tetrahydrofuran, and then adding ethyl acetate with one fifth volume ratio to prepare a solution;
(3) and (3) at room temperature, injecting the solution into a glass tube, putting the glass tube into an oven to naturally volatilize the solvent, then carrying out vacuum drying to obtain the glass tube coated with the fluorescent film, and then storing the glass tube in a dark place.
The glass tube is an organic transparent glass tube with the length of 20mm, the outer diameter of 5mm and the inner diameter of 1mm, and is ultrasonically washed for one hour by using pure water and ethanol in sequence before use, and is dried for 5 hours at 60 ℃ for later use.
The steroid-perylene diimide compound is applied to preparation of amphetamine drug detection products.
The fluorescent film is applied to detection of amphetamine drugs.
The fluorescent film is applied to the preparation of fluorescence sensing.
The key points of the technology of the invention are as follows: synthesizing a series of compounds which are formed by connecting different steroids with perylene diimide precursors through different connecting arms, and preparing the compounds into a film with a fluorescent response function to amphetamine drugs.
Has the advantages that: compared with the prior art, the invention has the following advantages: (1) the invention discloses a series of fluorescent compounds with a good induction function on phenylpropylamine drugs, which are synthesized by connecting different steroids with perylene diimide through a connecting arm, and are prepared into fluorescent films which are applied to the field of drug detection. The prepared fluorescent film has high fluorescence quantum yield, low detection limit, excellent stability and repeated use times. The obtained fluorescent thin-film device is matched with a customized portable fluorescent detector for use, so that drugs such as ice toxin and the like can be rapidly, conveniently and sensitively detected, and the efficiency of the work such as drug inspection and the like is further improved. (2) The invention also discloses a preparation method of the fluorescent compound with the response function to the amphetamine drugs, which has the advantages of low raw material price, simple reaction and good stability, and is suitable for batch reaction and mass synthesis. (3) The invention also discloses a method for preparing a fluorescent film by adopting the fluorescent compound, which is to attach the steroid-perylene diimide compound to the inner layer of the glass tube to obtain the fluorescent sensing component capable of quickly responding to the phenylpropylamine drugs, thereby realizing the quick and sensitive detection of the phenylpropylamine drug steam.
Drawings
FIG. 1 is a graph of the ultraviolet fluorescence spectrum of a chloroform solution (10 μ M) of a β -sitosterol-perylene diimide fluorescent compound prepared in the present invention;
fig. 2 is a fluorescence change curve (three cycles) of the beta-sitosterol-perylene diimide fluorescence sensing film prepared by the invention under methamphetamine vapor.
Detailed Description
The technical scheme of the invention is further explained in detail by combining the attached drawings and examples.
Example 1
1) Under the protection of nitrogen, 10g of beta-sitosterol is dissolved in 50ml of anhydrous tetrahydrofuran, 12.4g of anhydrous sodium carbonate is added, the mixture is cooled to 0 ℃, 13.9g of triphosgene is dissolved in 20ml of anhydrous tetrahydrofuran, the mixture is dropwise added at the speed of 20 drops/minute in an ice bath, and after the dropwise addition is finished, the mixture is reacted for two hours in an ice bath, and then the mixture is stirred and reacted for 12 hours at room temperature. Diluting the reaction product with hexane after the reaction is finished, performing suction filtration, concentrating the filtrate under reduced pressure, separating the crude product with petroleum ether/dichloromethane (4: 1) chromatographic column to obtain light yellow oily compound 8.8g, namely beta-sitosterol chloroformate, ESI-MS (m/z): 477.27[ M + H ] +. The reaction equation is as follows:
2) under the protection of nitrogen, 0.67g of ethanolamine is dissolved in 20mL of trichloromethane, the solution is stirred at room temperature until the solution is uniform and transparent, 4.7g of beta-sitosterol chloroformate is dissolved in 25mL of trichloromethane, the solution is slowly dripped into a reaction bottle at the speed of 5 drops/minute in an ice bath, and after the dripping is finished, the reaction is continuously stirred at room temperature for 12 hours. After the reaction is finished, washing three times by using dilute hydrochloric acid solution, washing three times by using pure water, separating an organic phase, drying, washing by using petroleum ether, and preparing 3.5g of beta-sitosterol ethanolamine white solid, ESI-MS (m/z): 502.55[ M + H ] +. Wherein n is 2. The reaction equation is as follows:
3) under the protection of nitrogen, 8g of 3, 4, 9, 10-perylenetetracarboxylic dianhydride and 17g of 12-aminododecanoic acid are added into 50ml of N-methylpyrrolidone, stirred at room temperature until the solution is uniform, and then refluxed and reacted at 110 ℃ for 12 hours. And after the reaction is finished, cooling to room temperature, pouring into 200mL of 0.5mol/L sodium hydroxide solution, stirring for 0.5 hour, performing suction filtration, washing filter residues with acetic acid for 0.5 hour, performing suction filtration, washing with acetic acid twice, and performing suction filtration to obtain 16g of a dark red solid compound, namely the perylene diimide-dodecanoic acid. 1H NMR (300MHz, Chloroform-d + CF3COOH) δ 8.77(d, J ═ 8.0Hz, 4H), 8.71(d, J ═ 8.2Hz, 4H), 4.27(t, J ═ 7.8Hz, 4H), 2.48(t, J ═ 7.5Hz, 4H), 1.75(dt, J ═ 27.6, 7.4Hz, 8H), 1.50-1.27(m, 28H). Wherein m is 11. The reaction equation is as follows:
4) under the protection of nitrogen, 7.8g of perylene diimide-dodecanoic acid is added into 25mL of thionyl chloride, and after the reflux is carried out for 5 hours at 100 ℃, after the reaction is completed, thionyl chloride is removed by rotary evaporation, and vacuum drying is carried out for 2 hours at 60 ℃ to obtain 8g of black red solid, namely perylene diimide-dodecyl acyl chloride, which is directly used for the next reaction without purification. Wherein m is 11. The reaction equation is as follows:
5) under the protection of nitrogen, 1.9g of perylene diimide-dodecyl acyl chloride and 3.5g of beta-sitosterol ethanolamine are dissolved in dichloromethane, after the suspension is stirred to be uniform, anhydrous potassium carbonate is added, reflux reaction is carried out for 12 hours at 55 ℃, after the reaction is finished, filtration is carried out, a solvent is removed, the obtained solid is subjected to column chromatography separation by using dichloromethane and acetone as eluent, wherein the ratio of the dichloromethane to the acetone is 15: 1, and 0.51g of red solid compound is prepared, namely the target product. Wherein m is 11, n is 2, and R is beta-sitosterol. 1H NMR (300MHz, Chloroform-d) δ 8.53(dd, J ═ 7.9, 1.5Hz, 4H), 8.39(dd, J ═ 8.1, 2.3Hz, 4H), 5.37(d, J ═ 5.0Hz, 2H), 4.91(s, 2H), 4.51(dt, J ═ 11.8, 6.2Hz, 2H), 4.17(td, J ═ 11.0, 10.0, 6.6Hz, 8H), 3.56 to 3.34(m, 4H), 2.32(dt, J ═ 10.5, 7.5Hz, 8H), 2.06 to 0.76(m, 120H), 0.67(s, 6H), MALDI-MS: 1755.83[ M + H ] +. The reaction equation is as follows:
the ultraviolet fluorescence spectrogram of the chloroform solution (10 mu M) of the target compound is shown in figure 1, and the compound has a strong fluorescence value and a large stocks displacement, so that the compound has low background fluorescence interference and solves the limitation of other fluorescent materials.
6) Dissolving 10mg of the target compound in 5.7mL of tetrahydrofuran, oscillating with ultrasound to completely dissolve the target compound, preparing 1mmol/L of mother liquor, and placing the mother liquor in a constant-temperature water bath kettle at 30.0 ℃ to be kept away from light for later use. And (2) putting 2mL of mother liquor into a centrifugal tube, adding 2mL of tetrahydrofuran, adding 0.8mL of ethyl acetate, uniformly shaking, injecting 15 mu L of mother liquor into a clean glass tube at room temperature of 25 ℃, putting the glass tube into a 45 ℃ oven to naturally volatilize the solvent, vacuumizing to 0.1MPa at 45 ℃ and drying for 20 minutes to remove the residual solvent after the solvent is volatilized, thus obtaining the fluorescent film with the response function to the phenylpropylamine narcotic drugs.
The response curve of the obtained fluorescent film to the phenylpropylamine drugs is shown in fig. 2, and it can be seen that the fluorescent film prepared by the method is sensitive to the drugs, and the fluorescence performance is reduced a little after three cycles, which indicates that the film can be repeatedly used for many times, and can realize large-scale, sensitive and rapid drug screening. It is worth noting that the film forming mode of the patent uses mild conditions, for example, reagents are tetrahydrofuran and ethyl acetate with low toxicity, the temperature is 45 ℃, compared with film forming conditions of other materials, the patent uses toxic reagents such as benzene and the like, and high-temperature and high-pressure environments, and the like, and the patent has the advantages of being simple, easy to obtain, non-toxic, environment-friendly and the like.
Example 2
1) Under the protection of nitrogen, 10g of stigmasterol is dissolved in 50ml of anhydrous tetrahydrofuran, 12.4g of anhydrous sodium carbonate is added, the mixture is cooled to 0 ℃, 13.9g of triphosgene is dissolved in 20ml of anhydrous tetrahydrofuran, the dropwise addition is carried out at the speed of 20 drops/minute in an ice bath, after the dropwise addition is finished, the ice bath reaction is carried out for 2 hours, and then the stirring reaction is carried out for 10 hours at the room temperature. After the reaction, the reaction product was diluted with hexane and filtered, the filtrate was concentrated under reduced pressure, and the crude product was separated by petroleum ether/dichloromethane (5: 1) column chromatography to give 9.3g of a transparent oily compound, namely stigmasterol chloroformate. ESI-MS (m/z): 475.61[ M + H ] +. The reaction equation is as follows:
2) under the protection of nitrogen, 0.67g of ethanolamine is dissolved in 20mL of trichloromethane, the solution is stirred at room temperature until the solution is uniform and transparent, 4.7g of stigmasterol chloroformate is dissolved in 25mL of trichloromethane, the solution is slowly dripped into a reaction bottle at the speed of 5 drops/minute in an ice bath, and after the dripping is finished, the reaction is continuously stirred at room temperature for 12 hours. After the reaction is finished, washing three times by using a dilute hydrochloric acid solution, washing three times by using pure water, separating an organic phase, drying, and washing by using petroleum ether to prepare 3.7g of stigmasterol ethanolamine white solid. ESI-MS (m/z): 500.03[ M + H ] +. Wherein n is 2. The reaction equation is as follows:
3) under the protection of nitrogen, 1.9g of perylene diimide-dodecyl acyl chloride and 3.5g of stigmasterol ethanolamine are dissolved in dichloromethane, after the suspension is stirred to be uniform, anhydrous potassium carbonate is added, reflux reaction is carried out overnight at 55 ℃, after the reaction is finished, filtration is carried out, the solvent is removed, the obtained solid is subjected to column chromatography separation by using dichloromethane and acetone as eluent, wherein the ratio of dichloromethane to acetone is 15: 1, and 0.46g of red solid is prepared, namely the target product. MALDI-TOF MS: 1751.88[ M + H] + . Wherein m is 11, n is 2, and R is stigmasterol. The reaction equation is as follows:
4) other steps are similar to those of example 1, and a fluorescent sensing film is prepared.
Example 3
1) Under the protection of nitrogen, 10g of ergosterol is dissolved in 50ml of anhydrous tetrahydrofuran, 12.4g of anhydrous sodium carbonate is added, the mixture is cooled to 0 ℃, 13.9g of triphosgene is dissolved in 20ml of anhydrous tetrahydrofuran, the mixture is dropwise added at the speed of 20 drops/minute in an ice bath, after the dropwise addition is finished, the ice bath reaction is carried out for 2 hours, and then the stirring reaction is carried out for 12 hours at room temperature. After the reaction, the reaction product is diluted by hexane and filtered, the filtrate is taken for decompression and concentration, and the crude product is separated by a petroleum ether/dichloromethane (4: 1) chromatographic column to prepare 6.7g of a light yellow oily compound, namely ergosterol chloroformate. ESI-MS (m/z): 459.60[ M + H ] +. The reaction equation is as follows:
2) under the protection of nitrogen, 0.67g of ethanolamine is dissolved in 20mL of trichloromethane, the solution is stirred at room temperature until the solution is uniform and transparent, 6.7g of ergosterol chloroformate is dissolved in 25mL of trichloromethane, the solution is slowly dripped into a reaction bottle at the speed of 5 drops/1 min under ice bath, and after the dripping is finished, the reaction is continuously stirred at room temperature for 12 hours. After the reaction, washing with dilute hydrochloric acid solution for three times, washing with pure water for three times, separating the organic phase, drying, and washing with petroleum ether to obtain 4.9g of ergosterol ethanolamine white solid. ESI-MS (m/z): 484.73[ M + H ] +. Wherein n is 2. The reaction equation is as follows:
3) under the protection of nitrogen, 1.9g of perylene diimide-dodecyl acyl chloride and 3.3g of ergosterol ethanolamine are dissolved in dichloromethane, after the suspension is stirred to be uniform, anhydrous potassium carbonate is added, reflux reaction is carried out overnight at 55 ℃, after the reaction is finished, filtration is carried out, a solvent is removed, the obtained solid is subjected to column chromatography separation by using dichloromethane and acetone as eluent, wherein the ratio of dichloromethane to acetone is 15: 1, and 0.60g of red solid is prepared, namely the target product. MALDI-TOF MS: 1719.29[ M + H ] +. Wherein m is 11, n is 2, and R is ergosterol. The reaction equation is as follows:
4) other steps are similar to those of example 1, and a fluorescent sensing film is prepared.
Example 4
1) Under the protection of nitrogen, 10g of dihydrocholesterol is dissolved in 50ml of anhydrous tetrahydrofuran, 12.4g of anhydrous sodium carbonate is added, the mixture is cooled to 0 ℃, 13.9g of triphosgene is dissolved in 20ml of anhydrous tetrahydrofuran, the mixture is dropwise added at the speed of 20 drops/minute in an ice bath, after the dropwise addition is finished, ice bath reaction is carried out for 2 hours, and then stirring reaction is carried out for 12 hours at room temperature. After the reaction, the reaction product was diluted with hexane and filtered, the filtrate was concentrated under reduced pressure, and the crude product was separated by petroleum ether/dichloromethane (5: 1) column chromatography to obtain 8.2g of a white solid compound, dihydrocholesterol chloroformate. ESI-MS (m/z): 451.43[ M + H ] +. The reaction equation is as follows:
2) under the protection of nitrogen, 0.67g ethanolamine is dissolved in 20mL chloroform, the solution is stirred at room temperature until the solution is uniform and transparent, 8.2g dihydrocholesterol chloroformate is dissolved in 25mL chloroform, the solution is slowly dripped into a reaction bottle at the speed of 5 drops/minute under ice bath, and after the dripping is finished, the reaction is continuously stirred at room temperature for 12 hours. After the reaction, the mixture was washed three times with a dilute hydrochloric acid solution and three times with pure water, the organic phase was separated, dried and washed with petroleum ether to prepare 6.5g of dihydrocholestroethanolamine white solid. ESI-MS (m/z): 476.03[ M + H ] +. Wherein n is 2. The reaction equation is as follows:
3) under the protection of nitrogen, 1.9g of perylene diimide-dodecyl acyl chloride and 3.3g of dihydrocholesterol ethanolamine are dissolved in dichloromethane, after the suspension is stirred to be uniform, anhydrous potassium carbonate is added, reflux reaction is carried out for 12 hours at 55 ℃, after the reaction is finished, filtration is carried out, a solvent is removed, the obtained solid is subjected to column chromatography separation by using dichloromethane and acetone as eluent, wherein the ratio of the dichloromethane to the acetone is 15: 1, and 0.47g of red solid is prepared, namely the target product. MALDI-TOF MS: 1703.45[ M + H ] +. Wherein m is 11, n is 2, and R is dihydrocholesterol. The reaction equation is as follows:
4) other steps are similar to those of example 1, and a fluorescent sensing film is prepared.
Example 5
1) Under the protection of nitrogen, 0.62g of n-propanolamine is dissolved in 20mL of trichloromethane, the solution is stirred at room temperature until the solution is uniform and transparent, 3.3g of beta-sitosterol chloroformate is dissolved in 25mL of trichloromethane, the solution is slowly dripped into a reaction bottle at the speed of 5 drops/minute in an ice bath, and after the dripping is finished, the reaction is continuously stirred at room temperature for 12 hours. After the reaction is finished, washing the mixture for three times by using a dilute hydrochloric acid solution, washing the mixture for three times by using pure water, separating an organic phase, drying the organic phase, and washing the organic phase by using petroleum ether to prepare 2.2g of beta-sitosterol-n-propanolamine white solid. ESI-MS (m/z): 516.88[ M + H ] +. Wherein n is 3. The reaction equation is as follows:
2) under the protection of nitrogen, dissolving 1.5g of perylene diimide-dodecyl acyl chloride and 2.2g of beta-sitosterol n-propanolamine in dichloromethane, stirring to make the suspension uniform, adding anhydrous potassium carbonate, refluxing at 55 ℃ for reaction overnight, filtering after the reaction is finished, removing the solvent, and performing column chromatography separation on the obtained solid by using dichloromethane and acetone as an eluent at the ratio of 15: 1 to prepare 0.39g of red solid, namely the target product. MALDI-TOF MS: 1783.16[ M + H ] +. Wherein m is 11, n is 3, and R is beta-sitosterol. The reaction equation is as follows:
3) other steps are similar to those of example 1, and a fluorescent sensing film is prepared.
Example 6
1) Under the protection of nitrogen, 8g of 3, 4, 9, 10-perylenetetracarboxylic dianhydride and 7.2g of 12-aminocaprylic acid are added into 50ml of N-methylpyrrolidone, stirred at room temperature until the solution is uniform, and then refluxed and reacted at 110 ℃ for 12 hours. After the reaction is finished, cooling to room temperature, pouring into 200mL of 0.5mol/L sodium hydroxide solution, stirring for 0.5 hour, performing suction filtration, washing filter residues with acetic acid for 0.5 hour, performing suction filtration, washing with acetic acid twice, and performing suction filtration to prepare 13.1g of dark red solid compound, namely perylene diimide-octanoic acid. MALDI-TOF MS: 675.76[ M + H ] +. Wherein m is 7. The reaction equation is as follows:
2) under the protection of nitrogen, 8g of perylene diimide-octanoic acid is added into 25mL of thionyl chloride, after the mixture is refluxed for 5 hours at 100 ℃, after the reaction is completed, thionyl chloride is removed by rotary evaporation, and vacuum drying is carried out for 2 hours at 60 ℃ to obtain 8.2g of black red solid, namely perylene diimide-nonyl acyl chloride, which is directly used for the next reaction without purification. Wherein m is 7. The reaction equation is as follows:
3) under the protection of nitrogen, 2g of perylene diimide-nonyl acyl chloride and 3.5g of beta-sitosterol n-propanolamine are dissolved in dichloromethane, after the suspension is stirred to be uniform, anhydrous potassium carbonate is added, reflux reaction is carried out for 12 hours at 55 ℃, after the reaction is finished, filtration is carried out, the solvent is removed, the obtained solid is subjected to column chromatography separation by using dichloromethane and acetone as eluent at the ratio of 15: 1, and 0.42g of red solid compound is prepared, namely the target product. MALDI-TOF MS: 1670.76[ M + H ] +. Wherein m is 7, n is 3, and R is beta-sitosterol. The reaction equation is as follows:
4) the other steps were similar to those in example 1, and a fluorescent sensor film was prepared.
Example 7
1) Under the protection of nitrogen, 1.03g of 5-amino-1-pentanol is dissolved in 20mL of chloroform, 4.7g of beta-sitosterol chloroformate is dissolved and slowly dripped into a reaction bottle at the speed of 5 drops/min, and after the dripping is finished, the stirring reaction is continued at room temperature for 12 hours. After the reaction is finished, washing the mixture for three times by using a dilute hydrochloric acid solution, washing the mixture for three times by using pure water, separating an organic phase, drying the organic phase, and washing the organic phase by using petroleum ether to prepare 3.1g of beta-sitosterol n-pentylamine white solid. ESI-MS (m/z): 544.62 [ M + H ] +. Wherein n is 5. The reaction equation is as follows:
2) under the protection of nitrogen, 8g of 3, 4, 9, 10-perylenetetracarboxylic dianhydride and 7.2g of 12-aminoundecanoic acid were added to 50ml of N-methylpyrrolidone, stirred at room temperature until the solution became homogeneous, and then reacted at 110 ℃ under reflux for 12 hours. After the reaction is finished, cooling to room temperature, pouring into 200mL of 0.5mol/L sodium hydroxide solution, stirring for 0.5 hour, performing suction filtration, washing filter residues with acetic acid for 0.5 hour, performing suction filtration, washing with acetic acid twice, and performing suction filtration to prepare 12.8g of dark red solid compound, namely perylene diimide undecanoic acid. MALDI-TOF MS: 759.38[ M + H ] +. Wherein m is 10. The reaction equation is as follows:
3) under the protection of nitrogen, 7.2g of perylene diimide-undecanoic acid is added into 25mL of thionyl chloride, and after refluxing for 5 hours at 100 ℃, after the reaction is completed, thionyl chloride is removed by rotary evaporation, and vacuum drying is carried out for 2 hours at 60 ℃ to obtain 7.3g of black red solid, namely perylene diimide-undecanoyl chloride, which is directly used for the next reaction without purification. Wherein m is 10. The reaction equation is as follows:
4) under the protection of nitrogen, 2.3g of perylene diimide-undecyl acyl chloride and 3.1g of beta-sitosterol n-pentaolamine are dissolved in dichloromethane, after the suspension is stirred to be uniform, anhydrous potassium carbonate is added, reflux reaction is carried out for 12 hours at 55 ℃, after the reaction is finished, filtration is carried out, the solvent is removed, the obtained solid is subjected to column chromatography separation by using dichloromethane and acetone as eluent at the ratio of 15: 1, and 0.48g of red solid compound is prepared, namely the target product. MALDI-TOF MS: 1811.69[ M + H ] +. Wherein m is 11, n is 5, and R is beta-sitosterol. The reaction equation is as follows:
5) other steps are similar to those of example 1, and a fluorescent sensing film is prepared.
In conclusion, experiments show that the fluorescent compound with the response function to the phenylpropylamine drugs has the advantages of easily available raw materials, low price, capability of large-scale synthesis production, mild and simple reaction conditions and high yield. The prepared fluorescent sensing film has the advantages of simple film forming conditions, low production cost, stable film forming property, high luminous efficiency, sensitive response to the phenylpropylamine and the like. The invention has important promoting significance for the fields of gas defense and gas control and the like.
Claims (10)
1. A steroid-perylene diimide compound is characterized in that the structure is as follows:
wherein m is 7-11; n is 2-5; r is selected from beta-sitosterol, stigmasterol, ergosterol or dihydrocholesterol.
2. The method of preparing a steroid-perylene diimide compound according to claim 1, characterized by comprising the steps of:
(1) adding anhydrous sodium carbonate into a reaction container, then adding an anhydrous tetrahydrofuran solution of sterol, stirring, dropwise adding an anhydrous tetrahydrofuran solution of triphosgene after ice bath, stirring and reacting for 1-3 hours in ice bath after dropwise adding is finished, and then stirring and reacting for 10-20 hours at room temperature; diluting the reactant with hexane after the reaction is finished, carrying out suction filtration, taking filtrate, carrying out reduced pressure concentration, and separating a crude product by using a chromatographic column to prepare a light yellow oily compound 1, namely sterol chloroformate;
(2) dissolving alkyl alcohol amine in trichloromethane, stirring at room temperature until the solution is uniform and transparent, slowly dropwise adding trichloromethane solution of sterol chloroformate in ice bath, and continuously stirring at room temperature after dropwise adding, and reacting for 10-20 hours; after the reaction is finished, washing with a dilute acid solution, then washing with water, separating an organic phase, and washing with petroleum ether to prepare a white solid compound 2;
(3) suspending 3, 4, 9, 10-perylenetetracarboxylic dianhydride and amino alkanoic acid in N-methylpyrrolidone, and carrying out reflux reaction at 100 ℃ and 130 ℃ for 8-12 hours; after the reaction is finished, cooling to room temperature, pouring into a sodium hydroxide dilute solution, stirring for 0.2-1.0 hour, then carrying out suction filtration, washing filter residues for 0.2-1.0 hour by using acetic acid, carrying out suction filtration, washing the filter residues by using an acetic acid solution, and preparing a dark red solid compound 3;
(4) dissolving the compound 3 in thionyl chloride, refluxing for 5 hours at 80-110 ℃, removing the dimethylsulfoxide by rotary evaporation, and drying in vacuum to obtain a black red solid, namely a compound 4;
(5) dissolving the compound 4 and the compound 1 in dichloromethane, adding anhydrous potassium carbonate, carrying out reflux reaction at 55 ℃ for 8-12 hours, filtering after the reaction is finished, removing an organic phase from filtrate, and carrying out column chromatography separation on obtained solids by using an eluent to prepare a red solid target compound.
3. The method for preparing a steroid-perylene diimide compound according to claim 2, wherein the chromatographic column in the step (1) is a petroleum ether/methylene chloride chromatographic column.
4. The method for producing a steroid-perylene diimide compound according to claim 2, wherein the eluent in the step (5) is a mixed solvent of dichloromethane and acetone.
5. The method for preparing a steroid-perylene diimide compound according to claim 4, wherein the volume ratio of the eluent in the step (5) is 20: 1-10: 1.
6. The method for producing a steroid-perylene diimide compound according to claim 2, wherein the steps (1) to (5) are performed under a nitrogen blanket.
7. A fluorescent film, which is prepared by dissolving and diluting the steroid-perylene diimide compound according to claim 1 in an organic solution, adding the solution into a transparent container, and evaporating the solvent.
8. The fluorescent film according to claim 7, which is prepared by the following steps:
(1) dissolving the steroid-perylene diimide compound solid of claim 1 in tetrahydrofuran to prepare a mother liquor;
(2) diluting the mother liquor by one time with tetrahydrofuran, and then adding ethyl acetate with one fifth volume ratio to prepare a solution;
(3) and (3) at room temperature, injecting the solution into a glass tube, putting the glass tube into an oven to naturally volatilize the solvent, then carrying out vacuum drying to obtain the glass tube coated with the fluorescent film, and then storing the glass tube in a dark place.
9. The steroid-perylene diimide compound as defined in claim 1, for use in preparation of amphetamine-based drug detection products.
10. The use of the fluorescent film of claim 7 for detecting amphetamine-type drugs.
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