CN109320507B - Chiral fluorescent compound based on quinoline amide folder and preparation method and application thereof - Google Patents
Chiral fluorescent compound based on quinoline amide folder and preparation method and application thereof Download PDFInfo
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- -1 quinoline amide Chemical class 0.000 title claims abstract description 111
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 144
- 239000000463 material Substances 0.000 claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 189
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 98
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 65
- 229920000642 polymer Polymers 0.000 claims description 62
- 229910052786 argon Inorganic materials 0.000 claims description 49
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 150000001412 amines Chemical class 0.000 claims description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 150000001263 acyl chlorides Chemical class 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- QACOLYQTPFGDLC-UHFFFAOYSA-N 2-(1,3-oxazol-2-yl)aniline Chemical compound NC1=CC=CC=C1C1=NC=CO1 QACOLYQTPFGDLC-UHFFFAOYSA-N 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 16
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 13
- JVSFQJZRHXAUGT-UHFFFAOYSA-N 2,2-dimethylpropanoyl chloride Chemical compound CC(C)(C)C(Cl)=O JVSFQJZRHXAUGT-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 abstract description 13
- 238000004020 luminiscence type Methods 0.000 abstract description 10
- 230000010287 polarization Effects 0.000 abstract description 7
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000000975 dye Substances 0.000 abstract description 2
- 241000589970 Spirochaetales Species 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 60
- 239000000243 solution Substances 0.000 description 49
- 125000004432 carbon atom Chemical group C* 0.000 description 39
- 239000000047 product Substances 0.000 description 37
- 238000001514 detection method Methods 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 30
- 125000000217 alkyl group Chemical group 0.000 description 20
- 238000005160 1H NMR spectroscopy Methods 0.000 description 18
- IJKZWPSOMRWQPA-UHFFFAOYSA-N 2-phenyl-1,3-oxazol-4-amine Chemical compound NC1=COC(C=2C=CC=CC=2)=N1 IJKZWPSOMRWQPA-UHFFFAOYSA-N 0.000 description 18
- 125000003107 substituted aryl group Chemical group 0.000 description 17
- 125000003118 aryl group Chemical group 0.000 description 16
- 125000004104 aryloxy group Chemical group 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 14
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 12
- 238000004440 column chromatography Methods 0.000 description 12
- 238000001748 luminescence spectrum Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 125000003342 alkenyl group Chemical group 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 8
- 238000001142 circular dichroism spectrum Methods 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 7
- 230000006698 induction Effects 0.000 description 6
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241001274216 Naso Species 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- FVIZARNDLVOMSU-UHFFFAOYSA-N ginsenoside K Natural products C1CC(C2(CCC3C(C)(C)C(O)CCC3(C)C2CC2O)C)(C)C2C1C(C)(CCC=C(C)C)OC1OC(CO)C(O)C(O)C1O FVIZARNDLVOMSU-UHFFFAOYSA-N 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- UOYPNWSDSPYOSN-UHFFFAOYSA-N hexahelicene Chemical compound C1=CC=CC2=C(C=3C(=CC=C4C=CC=5C(C=34)=CC=CC=5)C=C3)C3=CC=C21 UOYPNWSDSPYOSN-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- ZEXKKIXCRDTKBF-UHFFFAOYSA-N quinoline-2-carboxamide Chemical compound C1=CC=CC2=NC(C(=O)N)=CC=C21 ZEXKKIXCRDTKBF-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
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- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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Abstract
The invention discloses a chiral fluorescent compound of a quinoline amide folder and a preparation method and application thereof. The structural general formula of the compound is shown as the following formula I or formula II,the chiral fluorescent material has the characteristic of CPL luminescence, has good solubility in common organic solvents, and has yellow solution and good stability. The CPL signal intensity and the luminous intensity can be regulated and controlled according to the chain length of the compound, and the purpose of changing the CPL intensity and the luminous intensity by changing the length of the spirochete is achieved. The compound has wide application prospect in the fields of preparing chiral organic luminescent dye with circular polarization luminescent property, preparing chiral fluorescent probe and identifying fluorescence.
Description
Technical Field
The invention relates to the field of materials and preparation, in particular to a quinoline amide foldate-based chiral fluorescent compound and a preparation method and application thereof.
Background
The chiral organic fluorescent material is an organic material which has both chiral and luminescent properties. Chiral molecules with circular polarization light emission (CPL) characteristics have attracted attention in recent years due to their broad application prospects in the fields of photochemical materials, chiral identification, display devices, optical storage devices, chiral light emitting diodes, CPL lasers, asymmetric photocatalytic reactions and the like.
At present, organic molecules in the field are hot spots in the field due to the characteristics of simple structure, easy derivation, various varieties and the like. But because a higher asymmetry factor (g) cannot be obtainedlum) And quantum yield, limits the applications in the field of fluorescent materials.
The quinoline amide folds are different from the traditional helicene which forms a helical structure based on the main pi-pi stacking effect, and the folding effect is mainly driven by the three-center hydrogen bond effect formed by the N atoms on adjacent quinoline rings and amide hydrogen between the adjacent quinoline rings. A chromophore and a chiral induction center are introduced into a quinoline amide folder, and the folder generates the characteristics of circular polarization luminescence.
Disclosure of Invention
The technical problem to be solved by the application is to provide a quinoline amide folder-based chiral fluorescent compound, which has good CPL luminescence characteristics, and the CPL signal intensity and the luminescence intensity of the compound can be regulated and controlled according to the chain length of the compound.
Another technical problem to be solved by the present application is to provide a preparation method of a chiral fluorescent compound based on a quinoline amide foldate.
Another technical problem to be solved by the present application is to provide an application of a chiral fluorescent compound based on a quinoline amide foldate.
In order to solve the first technical problem, the invention adopts the following technical scheme:
a chiral fluorescent compound based on a quinoline amide folder is disclosed, wherein the structural general formula of the compound is shown as the following formula I or formula II,
in the formula I or formula II, R1Independently selected from alkyl, carbazolyl, aromatic group or substituted aromatic group with 1-15 carbon atoms, carbazoloxy, R2Independently selected from alkyl with 1-15 carbon atoms, carbazolyl, aryl, substituted aryl, carbazoloxy, aryloxy or substituted aryloxy, wherein the substituent of the substituted aryl is alkyl with 1-15 carbon atoms or alkenyl with 2-15 carbon atoms, R3Independently selected from alkyl with 1-15 carbon atoms, alkoxy with 1-15 carbon atoms, carbazolyl, aryl, substituted aryl, carbazoloxy, aryloxy or substituted aryloxy, wherein the one or more substituents of the substituted aryl are alkyl with 1-15 carbon atoms, alkenyl with 2-15 carbon atoms, alkynyl with 2-15 carbon atoms and alkoxy with 1-10 carbon atoms, R1、R2And R3Equal to or different from each other, n is an integer greater than 1.
As a further improvement in the technical solution, the compound comprises S-type enantiomer and R-type enantiomer; wherein,
the structural formula of the S-type enantiomer is shown as the following formula S-I or formula S-II,
the structural formula of the R enantiomer is shown as the following formula R-I or R-II,
formula S-I, formula S-II, formula R-I or formula R-II wherein R1Independently selected from alkyl, carbazolyl, aromatic group or substituted aromatic group with 1-15 carbon atoms, R2Independently selected from alkyl with 1-15 carbon atoms, carbazolyl, aryl, substituted aryl, carbazoloxy, aryloxy or substituted aryloxy, wherein the substituent of the substituted aryl is alkyl with 1-15 carbon atoms or alkenyl with 2-15 carbon atoms, R3Independently selected from alkyl with 1-15 carbon atoms, alkoxy with 1-15 carbon atoms, carbazolyl, aryl, substituted aryl, carbazoloxy, aryloxy or substituted aryloxy, wherein the one or more substituents of the substituted aryl are alkyl with 1-15 carbon atoms, alkenyl with 2-15 carbon atoms, alkynyl with 2-15 carbon atoms and alkoxy with 1-10 carbon atoms, R1、R2And R3Equal to or different from each other, n is an integer greater than 1.
As a further improvement of the technical scheme, R is1Selected from isobutyl, n is 4, 8 or 16, R2Is methyl, said R3Is a tert-butyl group.
A preparation method of a chiral fluorescent compound based on a quinoline amide folder, wherein the compound is shown as the formula I, and the preparation method comprises the following steps:
1) under the protection of argon, 4-substituted chiral 2- (2-aminophenyl) oxazole is dissolved in anhydrous dichloromethane, and N, N-diisopropylethylamine is added as alkali to obtain a solution a; dissolving carboxylic acid of the 4-isobutoxy-8-amino-2-carboxyl quinoline amide polymer in anhydrous dichloromethane to obtain a solution b; mixing the solution a and the solution b and stirring to obtain a single chiral quinoline amide polymer;
2) dissolving the single-chiral quinoline amide polymer obtained in the step 1) and 10% palladium-carbon in ethyl acetate in a hydrogen atmosphere, and heating and stirring to obtain amine of the single-chiral quinoline amide polymer;
3) under the protection of argon, anhydrous dichloromethane is used as a solvent, N, N-diisopropylethylamine is used as a base, and the amine of the single chiral quinoline amide polymer obtained in the step 2) and pivaloyl chloride are stirred at room temperature for 2-4 hours to obtain the compound shown in the formula I.
As a further improvement of the technical scheme, in the step 1), the ratio of acyl chloride of N, N-diisopropylethylamine and 4-isobutoxy-8-amino-2-carboxyl quinoline amide polymer to 4-substituted chiral 2- (2-aminophenyl) oxazole is 2-100: 1: 0.85-10;
in the step 2), the pressure of hydrogen is 0.8-1.5 MPa, the heating temperature is 40-60 ℃, the heating and stirring time is 6-15 hours, and the mass ratio of the single chiral quinoline amide polymer to 10% palladium-carbon is 10: 1-3;
in the step 3), the mass ratio of the pivaloyl to the amine of the single chiral quinoline amide polymer is 1-500: 1.
A preparation method of a chiral fluorescent compound based on a quinoline amide folder, wherein the compound is shown as the formula I, and the preparation method comprises the following steps:
1) under the protection of argon, anhydrous dichloromethane is used as a solvent, N, N-diisopropylethylamine is used as a base, and the amine of the 4-isobutoxy-8-amino-2-carboxyl quinoline amide polymer and pivaloyl chloride are stirred at room temperature for 2-4 hours to obtain a fluorescence product pivaloyl quinoline amide polymer;
2) dissolving the pivaloyl quinoline amide polymer obtained in the step 1) in a mixed solvent of tetrahydrofuran and methanol, dissolving NaOH in deionized water, adding the dissolved NaOH, and heating and stirring for 1-4 h to obtain carboxylic acid of the pivaloyl quinoline amide polymer;
3) under the protection of argon, dissolving the carboxylic acid of the pivaloyl quinoline amide polymer obtained in the step 2) in anhydrous dichloromethane, adding oxalyl chloride, and stirring at room temperature to obtain acyl chloride of the pivaloyl quinoline amide polymer;
4) under the protection of argon, 4-substituted chiral 2- (2-aminophenyl) oxazole is dissolved in anhydrous dichloromethane, and N, N-diisopropylethylamine is added to obtain a solution c; dissolving acyl chloride of the pivaloyl quinoline amide polymer obtained in the step 3) in anhydrous dichloromethane to obtain a solution d, mixing the solutions c and d, and stirring to obtain the compound shown in the formula I.
As a further improvement of the technical solution,
in the step 1), the ratio of amine of N, N-diisopropylethylamine and 4-isobutoxy-8-amino-2-carboxyl quinoline amide polymer to pivaloyl chloride is 2-100: 1: 0.85-10;
in the step 2), the mass ratio of tetrahydrofuran, methanol and water is 5-100: 1-100: 0.1-50; the mass ratio of the pivaloyl quinoline amide polymer to the sodium hydroxide is 1: 10-1: 20;
in the step 3), the mass ratio of the carboxylic acid to the oxalyl chloride of the pivaloyl quinoline amide polymer is 1: 2-100;
in the step 4), the ratio of the acyl chloride of the pivaloyl quinoline amide polymer to the substance of 4-substituted chiral 2- (2-aminophenyl) oxazole is 1: 0.85-1.2.
A preparation method of a chiral fluorescent compound based on a quinoline amide folder, wherein the compound is shown as the formula II, and the preparation method comprises the following steps:
1) under the protection of argon, dissolving 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid in anhydrous dichloromethane, adding oxalyl chloride, and stirring at room temperature to obtain 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid chloride;
2) under the protection of argon, dissolving amine of the chiral quinoline amide polymer in anhydrous dichloromethane, and adding N, N-diisopropylethylamine to obtain a solution e; dissolving the 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid chloride obtained in the step 1) in anhydrous dichloromethane to obtain a solution f; and mixing and stirring the solution e and the solution f to obtain the compound shown in the formula II.
As a further improvement of the technical scheme, in the step 1), the mass ratio of the 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid to oxalyl chloride is 1: 5-1000; (ii) a
In the step 2), the ratio of the amounts of the acyl chloride of 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid, N-diisopropylethylamine and the 4-substituted chiral 2- (2-aminophenyl) oxazole is 1:5 to 1000:2 to 10.
The invention also discloses application of the quinoline amide foldamer-based chiral fluorescent compound in the fields of preparation of chiral organic luminescent materials, preparation of chiral fluorescent probes and fluorescent identification.
Any range recited herein is intended to include the endpoints and any number between the endpoints and any subrange subsumed therein or defined therein.
The starting materials of the present invention are commercially available, unless otherwise specified, and the equipment used in the present invention may be any equipment conventionally used in the art or may be any equipment known in the art.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides chiral organic molecules with circular polarization luminescence and a preparation method thereof. The chiral fluorescent material provided by the invention has the characteristic of CPL luminescence, has good solubility in common organic solvents, and has yellow solution and good stability. The CPL signal intensity and the luminous intensity of the chiral fluorescent material can be regulated and controlled according to the chain length of a compound shown by a formula S-I, R-I, S-II or R-II. When the value of n is larger, the CPL signal is stronger, and the luminous intensity is increased, so that the purpose of changing the CPL intensity and the luminous intensity by changing the length of the spiral body is achieved. The compounds have wide application prospects in the fields of preparation of chiral organic luminescent dyes with circular polarization luminescent properties, chiral fluorescent probes and fluorescent identification.
Drawings
FIG. 1 is a circular dichroism spectrum of the compound prepared in example 1;
FIG. 2 is a circular dichroism spectrum of the compound prepared in example 2;
FIG. 3 is a chart of the circular dichroism spectrum of the compound prepared in example 3;
FIG. 4 is a chart of the circular dichroism spectrum of the compound prepared in example 4;
FIG. 5 is a chart of the circular dichroism spectrum of the compound prepared in example 5;
FIG. 6 is a circular dichroism spectrum of the compound prepared in example 6;
FIG. 7 is a circular polarized luminescence spectrum of the compound prepared in example 1;
FIG. 8 is a circularly polarized luminescence spectrum of the compound prepared in example 2;
FIG. 9 is a circularly polarized luminescence spectrum of the compound prepared in example 3;
FIG. 10 is a circularly polarized luminescence spectrum of the compound prepared in example 4;
FIG. 11 is a circularly polarized luminescence spectrum of the compound prepared in example 5;
FIG. 12 is a circularly polarized luminescence spectrum of the compound prepared in example 6;
FIG. 13 is a graph of asymmetry factor as a function of wavelength for the circularly polarized luminescence spectrum of the compound prepared in example 1;
FIG. 14 is a graph of asymmetry factor as a function of wavelength for the circularly polarized luminescence spectrum of the compound prepared in example 2;
FIG. 15 is a graph of asymmetry factor as a function of wavelength for the circularly polarized luminescence spectrum of the compound prepared in example 3;
FIG. 16 is a graph of the asymmetry factor as a function of wavelength for the circularly polarized luminescence spectrum of the compound prepared in example 4;
FIG. 17 is a graph of the asymmetry factor as a function of wavelength for the circularly polarized luminescence spectrum of the compound prepared in example 5;
FIG. 18 is a graph of asymmetry factor as a function of wavelength for the circularly polarized luminescence spectrum of the compound prepared in example 6.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The application relates to a chiral fluorescent compound based on a quinoline amide folder, the structural general formula of a racemate of the compound is shown as the following formula I or formula II,
in the formula I or formula II, R1Independently selected from alkyl, carbazolyl, aromatic group or substituted aromatic group with 1-15 carbon atoms, carbazoloxy, R2Independently selected from alkyl with 1-15 carbon atoms, carbazolyl, aryl, substituted aryl, carbazoloxy, aryloxy or substituted aryloxy, wherein the substituent of the substituted aryl is alkyl with 1-15 carbon atoms or alkenyl with 2-15 carbon atoms, R3Independently selected from alkyl with 1-15 carbon atoms, alkoxy with 1-15 carbon atoms, carbazolyl, aryl, substituted aryl, carbazoloxy, aryloxy or substituted aryloxy, wherein the one or more substituents of the substituted aryl are alkyl with 1-15 carbon atoms, alkenyl with 2-15 carbon atoms, alkynyl with 2-15 carbon atoms and alkoxy with 1-10 carbon atoms, R1、R2And R3Equal to or different from each other, n is an integer greater than 1.
According to certain embodiments of the present application, the above compounds include the S enantiomer and the R enantiomer.
Wherein the structural formula of the S-type enantiomer is shown as the following formula S-I or formula S-II,
the structural formula of the R enantiomer is shown as the following formula R-I or R-II,
formula S-I, formula S-II, formula R-I or formula R-II wherein R1Independently selected from alkyl, carbazolyl and aryl with 1-15 carbon atomsAn aryl or substituted aryl, carbazoloxy; r2Independently selected from alkyl with 1-15 carbon atoms, carbazolyl, aryl, substituted aryl, carbazoloxy, aryloxy or substituted aryloxy, wherein the substituent of the substituted aryl is alkyl with 1-15 carbon atoms or alkenyl with 2-15 carbon atoms; r3Independently selected from alkyl with 1-15 carbon atoms, alkoxy with 1-15 carbon atoms, carbazolyl, aryl, substituted aryl, carbazoloxy, aryloxy or substituted aryloxy, wherein the one or more substituents of the substituted aryl are alkyl with 1-15 carbon atoms, alkenyl with 2-15 carbon atoms, alkynyl with 2-15 carbon atoms and alkoxy with 1-10 carbon atoms, R1、R2And R3Equal to or different from each other, n is an integer greater than 1.
According to certain embodiments of the present application, the compounds of formula S-I have the structures shown below as formulas S-I1 through S-I3:
in the above formulas S-I1 and S-I2, R2Independently selected from methyl, isopropyl, phenyl or benzyl.
According to certain embodiments of the present application, the compounds of formula S-II have the following structures S-II1 through S-II 3:
according to certain embodiments of the present application, the compounds of formula R-I have the following structures R-I1 through R-I3:
according to certain embodiments of the present application, the compounds of formula R-II have the structure of formula R-II1 to
R-II 3:
still further, according to certain embodiments of the present application, the compounds of formula S-I1 are of the following formulae S-I1-a through S-I1-d:
the compounds shown in the formulas S-I1 are shown in the formulas S-I1-a to S-I1-d, chiral amine has chiral induction effect on quinoline amide folder, and the chiral induction is complete, so that the quinoline amide folder with optical activity has single chirality and shows circular polarization luminescence.
Still further, according to certain embodiments of the present application, the compounds of formula S-I2 are of the following formulae S-I2-a through S-I2-d:
the compounds shown in the formulas S-I1 are shown in the formulas S-I1-a to S-I1-d, chiral amine has chiral induction effect on quinoline amide folder, and the chiral induction is complete, so that the quinoline amide folder with optical activity has single chirality and shows circular polarization luminescence. Furthermore, the chiral induction effect is amplified due to the increased chain length of the quinoline amide fold, and the effect of circularly polarized luminescence is also amplified.
The application relates to a preparation method of a quinoline amide foldate-based chiral fluorescent compound, which is shown as the formula I and comprises the following steps:
1) under the protection of argon, 4-substituted chiral 2- (2-aminophenyl) oxazole is dissolved in anhydrous dichloromethane, and N, N-diisopropylethylamine is added as alkali to obtain a solution a; dissolving carboxylic acid of the 4-isobutoxy-8-amino-2-carboxyl quinoline amide polymer in anhydrous dichloromethane to obtain a solution b; mixing the solution a and the solution b and stirring to obtain a single chiral quinoline amide polymer;
2) dissolving the single-chiral quinoline amide polymer obtained in the step 1) and 10% palladium-carbon in ethyl acetate in a hydrogen atmosphere, and heating and stirring the mixture overnight to obtain amine of the single-chiral quinoline amide polymer;
3) under the protection of argon, anhydrous dichloromethane is used as a solvent, N, N-diisopropylethylamine is used as a base, and the amine of the single chiral quinoline amide polymer obtained in the step 2) and pivaloyl chloride are stirred at room temperature for 2-4 hours to obtain the compound shown in the formula I.
According to certain embodiments of the present application, in step 1), the ratio of the acyl chloride of the N, N-diisopropylethylamine, 4-isobutoxy-8-amino-2-carboxyquinoline amide multimer to the 4-substituted chiral 2- (2-aminophenyl) oxazole is 2-100: 1: 0.85-10; the preferred ratio is 2:1: 0.9. The applicant finds that the compound is prepared by using an acyl chloride condensation method, the reaction steps are simple, and the yield is considerable.
According to some embodiments of the present application, in the step 2), the pressure of hydrogen is 0.8 to 1.5 mpa, preferably 1.0 mpa, the heating temperature is 40 to 60 ℃, the heating and stirring time is 6 to 15 hours, and the mass ratio of the single chiral quinoline amide polymer to 10% palladium-carbon is 10:1 to 3; preferably 10: 1. The applicant finds that the synthesis scheme is simple and rapid in operation and post-treatment, high in yield, low in cost and high in atom conversion rate.
According to some embodiments of the present application, in step 3), the ratio of the amount of the substance of pivaloyl to the amine of the single chiral quinolinamide multimer is 1-500: 1, preferably 1.2: 1. The technical scheme has the advantages of simple operation, easily obtained raw materials and higher yield.
The reaction formula of the preparation method is as follows:
another preparation method of a quinoline amide foldate-based chiral fluorescent compound, which is shown as the formula I above, comprises the following steps:
1) under the protection of argon, anhydrous dichloromethane is used as a solvent, N, N-diisopropylethylamine is used as a base, and the amine of the 4-isobutoxy-8-amino-2-carboxyl quinoline amide polymer and pivaloyl chloride are stirred at room temperature for 2-4 hours to obtain a fluorescence product pivaloyl quinoline amide polymer;
2) dissolving the pivaloyl quinoline amide polymer obtained in the step 1) in a mixed solvent of tetrahydrofuran and methanol, dissolving NaOH in deionized water, adding the dissolved NaOH, and heating and stirring for 1-4 h to obtain carboxylic acid of the pivaloyl quinoline amide polymer;
3) under the protection of argon, dissolving the carboxylic acid of the pivaloyl quinoline amide polymer obtained in the step 2) in anhydrous dichloromethane, adding oxalyl chloride, and stirring at room temperature to obtain acyl chloride of the pivaloyl quinoline amide polymer;
4) under the protection of argon, 4-substituted chiral 2- (2-aminophenyl) oxazole is dissolved in anhydrous dichloromethane, and N, N-diisopropylethylamine is added to obtain a solution c; dissolving acyl chloride of the pivaloyl quinoline amide polymer obtained in the step 3) in anhydrous dichloromethane to obtain a solution d, mixing the solutions c and d, and stirring to obtain the compound shown in the formula I.
According to some embodiments of the present application, in step 1), the ratio of the amine of the N, N-diisopropylethylamine, 4-isobutoxy-8-amino-2-carboxyquinoline amide polymer to the pivaloyl chloride is 2-100: 1: 0.85-10; preferably 2:1: 1.2. The technical scheme has the advantages of simple operation, easily obtained raw materials and higher yield.
According to some embodiments of the present application, in the step 2), the ratio of the amounts of the tetrahydrofuran, the methanol and the water is 5 to 100:1 to 100:0.1 to 50; preferably 10:1: 1; the ratio of the amount of the pivaloyl quinoline amide polymer to the amount of the sodium hydroxide is 1:10 to 1: 20. The operation scheme is simple and easy to implement, the post-treatment purification is simple, and the yield is considerable.
According to certain embodiments of the present application, in step 3), the ratio of the mass of carboxylic acid to oxalyl chloride of the pivaloyl quinoline amide multimer is 1:2 to 100; preferably 1: 2. The applicant finds that the reaction of oxalyl chloride and carboxylic acid is simple in reaction operation and post-treatment and considerable in yield.
According to certain embodiments of the present application, in said step 4), the ratio of the amount of the acid chloride of the pivaloyl quinoline amide multimer to the amount of the substance of the 4-substituted chiral 2- (2-aminophenyl) oxazole is 1:0.85 to 1.2, preferably 1: 0.9. The applicant finds that the compound prepared by using the acyl chloride condensation method has high reaction activity, simple reaction steps and considerable yield.
The reaction formula of the preparation method is as follows:
the application relates to a preparation method of a quinoline amide foldate-based chiral fluorescent compound, which is shown as the formula II and comprises the following steps:
1) under the protection of argon, dissolving 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid in anhydrous dichloromethane, adding oxalyl chloride, and stirring at room temperature to obtain 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid chloride;
2) under the protection of argon, dissolving amine of the chiral quinoline amide polymer in anhydrous dichloromethane, and adding N, N-diisopropylethylamine to obtain a solution e; dissolving the 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid chloride obtained in the step 1) in anhydrous dichloromethane to obtain a solution f; and (4) mixing the solutions e and f, and stirring to obtain the compound shown in the formula II.
According to certain embodiments of the present application, in step 1), the mass ratio of 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid to oxalyl chloride is 1:5 to 1000, preferably 1: 5. The applicant finds that the reaction of oxalyl chloride and a phenanthroline dicarboxylic acid compound has high reaction activity, simple reaction steps and considerable yield.
According to certain embodiments of the present application, in the step 2), the ratio of the amounts of the 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid chloride, N-diisopropylethylamine and the 4-substituted chiral 2- (2-aminophenyl) oxazole in the substance is 1:5 to 1000:2 to 10, preferably 1:5: 2. The applicant finds that the compound prepared by using the acyl chloride condensation method has high reaction activity, simple reaction steps and considerable yield.
The reaction formula of the preparation method is as follows:
the chiral fluorescent compound based on the quinoline amide folder has wide application prospects in the fields of preparation of chiral organic luminescent materials, preparation of chiral fluorescent probes and fluorescent identification.
The following examples further illustrate the invention. The reagents used in the examples of the present invention are commercially available unless otherwise specified.
Example 1
Preparation of Compounds of formula S-I1 and formula R-I1
The reaction formula is as follows:
the preparation process comprises the following steps:
1) 254mg of A was placed in a 50mL two-necked flask, and the above-mentioned compound was dissolved in 10mL of anhydrous dichloromethane under an argon atmosphere, and 31. mu.L of N, N-diisopropylethylamine and 25. mu.L of pivaloyl chloride were slowly added in this order by means of a syringe, followed by stirring at room temperature for 3 hours. The product was isolated by column chromatography as yellow powder product B in 93% yield;
2) dissolving 200mg of B in a mixed solvent of 10mL of tetrahydrofuran and 2mL of methanol in a 50mL eggplant-shaped bottle, dissolving 72mg of NaOH solid in 2mL of deionized water, slowly dropwise adding the obtained NaOH solution into the solution of B, heating the mixed solution in an oil bath at 40 ℃ for 2 hours, completely hydrolyzing the compound B, dropwise adding 1mol/L of dilute hydrochloric acid into the reacted solution, and reducing the pH of the reaction solution to 4-5; then extracting with a large amount of dichloromethane and deionized water, and using anhydrous NaSO for an organic phase4Drying, distilling under reduced pressure to remove the organic solvent to obtain a yellow solid, namely a product C, wherein the yield is 82%;
3) dissolving 200mg of C in 10mL of anhydrous dichloromethane in a 50mL two-mouth bottle under the protection of argon, adding 15 mu L of oxalyl chloride by using an injector, stirring at room temperature for two hours, distilling under reduced pressure to remove an organic solvent, continuously vacuumizing on a vacuum pump for two hours, and dissolving in 3mL of anhydrous dichloromethane under the protection of argon for later use; an amount of 0.9 equivalents of 4-R-yl-2- (2-aminophenyl) oxazole or R-4-R-2- (2-aminophenyl) oxazole in a 50mL two-necked flask was dissolved in anhydrous dichloromethane under argon and 31 μ L N, N-diisopropylethylamine was added, after which the above acid chloride solution was slowly added by syringe and stirred at room temperature overnight. Separating the product by column chromatography to obtain the compound of formula S-I1 or R-I1. The yield is 62-85%.
When the chiral aminophenyl oxazole is S-4-methyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula S-I1-a in 62% yield. The structure detection structure of the compound is as follows:1H NMR(400 MHz,CDCl3)δ13.18(s,1H),12.21(s,1H),11.81(s,1H),11.33(s,1H),9.14(s,1H), 8.77(d,1H),8.69(d,1H),8.63(d,1H),8.15(d,1H),8.09(d,1H),8.02(d,1H),7.97 (dd,2H),7.91(d,1H),7.67(dd,1H),7.61(dd,2H),7.52(dd,1H),7.34(m,2H),7.27 (d,1H),7.18(dd,1H),6.90(s,1H),6.81(s,1H),4.46(m,1H),4.36(m,1H), 4.14~4.21(m,2H),3.87~3.97(m,4H),3.06(t,1H),2.57(m,2H),2.46(m,1H), 2.20~2.37(m,4H),2.02(m,1H),1.19~1.35(m,24H),0.81(s,9H),0.48(d,3H).13C NMR(151MHz,CDCl3)δ176.40,163.53,163.03,162.87,162.52,162.48,162.19, 150.43,150.33,149.61,149.06,139.24,138.48,137.91,137.79,137.03,134.21, 134.10,133.72,131.75,129.66,128.41,128.05,127.47,127.00,126.74,126.69, 125.30,122.95,122.55,122.47,122.01,121.60,120.10,117.45,116.99,116.78, 116.46,116.39,116.16,116.11,115.85,114.09,100.05,99.90,98.70,98.09,75.50, 75.33,75.20,69.73,67.43,42.40,39.77,29.77,28.37,28.28,28.24,27.06,19.57, 19.40,19.33.MS(ESI)calculated for C71H76N10O10[M+H]+1229.5824, found 1229.5442; the results of the detection revealed that the above compound had a correct structure.
When the chiral aminophenyl oxazole is S-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula S-I1-b in yieldThe content was 85%. The structure detection structure of the compound is as follows:1H NMR(600 MHz,CDCl3)δ13.12(s,1H),12.18(s,1H),11.53(s,1H),11.28(s,1H),9.13(s,1H), 8.70(d,1H),8.68(d,1H),8.63(d,1H),8.12(d,1H),8.07(d,1H),8.00(d,1H),7.99 (d,1H),7.95(d,1H),7.91(d,1H),7.64-7.66(m,2H),7.59(dd,1H),7.54(td,1H), 7.27-7.34(m,4H),7.20(t,1H),6.91(s,1H),6.84(s,1H),6.64-6.47(m,2H),6.42(s, 1H),6.41(s,1H),6.34(t,1H),4.44(dd,1H),4.37(dd,1H),4.13-4.19(m,2H),3.95 (d,2H),3.90(d,1H),3.24(dd,1H),2.50-2.55(m,2H),2.30-2.40(m,3H),2.14(t, 1H),2.10(dd,1H),1.98(dd,1H),1.19-1.33(m,36H),0.80(s,11H).13C NMR(101 MHz,)δ176.41,163.64,163.56,163.37,163.17,162.72,162.56,162.34,161.95, 160.92,150.43,150.39,149.65,149.14,141.24,139.06,138.36,137.96,137.87, 137.83,134.18,134.09,133.96,133.74,131.85,129.73,128.15,127.09,127.06, 126.72,125.79,123.07,122.56,122.52,121.87,121.68,120.29,117.11,117.03, 116.77,116.45,116.26,115.90,114.19,99.89,98.72,98.07,75.54,75.45,75.41, 75.16,72.29,69.23,39.79,29.78,28.38,28.34,28.26,27.09,19.57,19.53,19.47, 19.40.Yield:83%.MS(ESI)calculated for[M+H]+1291.5975, found 1291.5975; the results of the detection revealed that the above compound had a correct structure.
When the chiral aminophenyl oxazole is S-4-isobutyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula S-I1-c in 68% yield.1H NMR(400MHz,CDCl3)δ13.26(s,1H), 12.23(s,1H),11.78(s,1H),11.35(s,1H),9.16(s,1H),8.74(d,1H),8.13(d,1H),8.63 (d,1H),8.14(d,1H),8.07(d,1H),8.01(d,1H),7.98(d,1H),7.97(d,1H),7.92(d, 1H),7.66(dd,1H),7.63(d,1H),7.62(d,1H),7.53(dd,1H),7.35(s,1H),7.34(d, 1H),7.32(s,1H),7.28(d,1H),7.19(dd,1H),6.91(s,1H),6.83(s,1H),4.43(dd,1H), 4.39(dd,1H)4.20(t,1H),4.16(t,1H),3.88-3.96(m,5H),3.20(t,1H),2.48-2.52(m, 2H),2.28-2.36(m,2H),2.22(dd,1H),1.90(dd,1H),1.20-1.33(m,50H),0.84(s,9H), 0.15(dd,6H).13C NMR(101MHz,CDCl3)δ176.42,163.59,163.10,162.79,162.63, 162.13,162.01,161.08,150.47,150.39,149.93,148.98,139.17,138.42,137.92, 137.78,134.10,134.07,133.95,133.69,131.60,129.67,128.09,126.98,126.85, 126.75,122.95,122.49,121.98,121.61,120.00,117.26,116.97,116.48,116.40, 116.15,116.09,115.87,114.09,99.93,98.84,97.91,75.51,75.46,75.33,75.20,71.68, 68.21,39.78,32.88,32.00,29.77,29.44,28.42,28.36,28.27,27.23,27.07,22.77, 20.66,19.56,19.53,19.46,19.42,19.33,18.31,17.47,14.20.Yield:76%.MS(ESI) calculated for[M+H]+1257.6131, found 1257.6149; the results of the detection revealed that the above compound had a correct structure.
When the chiral aminophenyl oxazole is S-4-benzyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula S-I1-d in 74% yield.1H NMR(600MHz,CDCl3)δ13.12(s,1H), 12.18(s,1H),11.53(s,1H),11.29(s,1H),9.13(s,1H),8.73(d,1H),8.67(d,1H), 8.64(d,1H),8.12(d,1H),8.07(d,1H),7.99(dd,2H),7.94(d,1H),7.89(d,1H),7.65 (m,3H),7.59(dd,1H),7.54(dd,1H),7.33(m,2H),7.29,(m,2H),7.20(dd,1H), 6.91(s,1H),6.84(s,1H),6.45(dd,2H),6.42(dd,2H),6.34(dd,1H),4.44(t,1H), 4.38(t,1H),4.16(m,2H),3.94(d,2H),3.94(d,2H),3.24(t,1H),2.53(m,2H), 2.34(m,4H),2.14(m,2H),1.98(dd,1H),1.19~1.32(m,24H),0.80(s,9H).13C NMR(151MHz,CDCl3)δ176.39,163.54,163.05,162.86,162.55,162.49,162.20, 161.98,161.03,150.45,150.36,149.65,149.09,139.25,138.50,137.94,137.81, 137.04,134.22,134.14,133.74,131.73,129.65,128.40,128.04,127.48,126.99, 126.73,126.68,125.30,122.92,122.57,122.49,122.03,121.63,120.09,117.44, 117.00,116.77,116.49,116.38,116.19,116.09,115.83,114.11,100.06,99.90,98.73, 98.12,75.50,75.33,75.21,69.72,67.41,42.37,39.76,29.75,28.38,28.28,28.23, 27.05,19.54,19.51,19.45,19.37,19.31.MS(ESI)calculated for[M+H]+1305.6131, found 1305.6149; the results of the detection revealed that the above compound had a correct structure.
When the chiral aminophenyl oxazole is R-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula R-I1. The yield was 78%.1H NMR(600MHz,CDCl3)δ13.12(s,1H),12.18 (s,1H),11.53(s,1H),11.28(s,1H),9.13(s,1H),8.70(d,1H),8.68(d,1H),8.64(d, 1H),8.13(d,1H),8.07(d,1H),8.00(d,1H),7.99(d,1H),7.95(d,1H),7.90(d,1H), 7.64-7.66(m,2H),7.59(dd,1H),7.54(td,1H),7.27-7.34(m,4H),7.20(t,1H),6.91 (s,1H),6.84(s,1H),6.64-6.47(m,2H),6.42(s,1H),6.41(s,1H),6.34(t,1H),4.44 (dd,1H),4.37(dd,1H),4.13-4.19(m,2H),3.95(d,2H),3.90(d,1H),3.24(dd,1H), 2.50-2.55(m,2H),2.30-2.40(m,3H),2.14(t,1H),2.10(dd,1H),1.98(dd,1H), 1.19-1.33(m,36H),0.80(s,11H).13C NMR(101MHz,)δ176.41,163.64,163.56, 163.37,163.17,162.72,162.56,162.34,161.95,160.92,150.43,150.39,149.65, 149.14,141.24,139.06,138.36,137.96,137.87,137.83,134.18,134.09,133.96, 133.74,131.85,129.73,128.15,127.09,127.06,126.72,125.79,123.07,122.56, 122.52,121.87,121.68,120.29,117.11,117.03,116.77,116.45,116.26,115.90, 114.19,99.89,98.72,98.07,75.54,75.45,75.41,75.16,72.29,69.23,39.79,29.78, 28.38,28.34,28.26,27.09,19.57,19.53,19.47,19.40.Yield:78%.MS(ESI) calculated for[M+H]+1291.5975, found 1291.5993; the results of the detection revealed that the above compound had a correct structure.
Example 2
Preparation of Compounds of formula S-I2 or R-I2
The reaction formula is as follows:
the preparation process comprises the following steps:
1) 490mg of E was added to a 50mL two-necked flask, and the above-mentioned compound was dissolved in 10mL of anhydrous dichloromethane under an argon atmosphere, and 31. mu.L of N, N-diisopropylethylamine and 15. mu.L of pivaloyl were slowly added in this order by means of a syringe, and the mixture was stirred at room temperature for 3 hours. The product was isolated by column chromatography as yellow powder of product F in 71% yield;
2) dissolving 400mg of F in a mixed solvent of 10mL of tetrahydrofuran and 2mL of methanol in a 50mL eggplant-shaped bottle, dissolving 140mg of NaOH solid in 2mL of deionized water, slowly dropwise adding the obtained NaOH solution into the solution of F, heating the mixed solution in an oil bath at 40 ℃ for 4 hours, completely hydrolyzing the compound F, dropwise adding 1mol/L of dilute hydrochloric acid into the reacted solution, and reducing the pH of the reaction solution to 4-5. Then extracting with a large amount of dichloromethane and deionized waterAnhydrous NaSO for organic phase4Drying, and distilling under reduced pressure to remove the organic solvent to obtain a yellow solid, namely a product G; the yield is 96%;
3) dissolving 300mg G in 10mL of anhydrous dichloromethane in a 50mL two-mouth bottle under the protection of argon, adding 10 mu L of oxalyl chloride by using an injector, stirring at room temperature for two hours, distilling under reduced pressure to remove an organic solvent, continuously vacuumizing on a vacuum pump for two hours, and dissolving in 3mL of anhydrous dichloromethane under the protection of argon for later use; the amount of substance 0.9 equivalents of 4-R-yl-2- (2-aminophenyl) oxazole was dissolved in anhydrous dichloromethane under argon in a 50mL two-necked flask and 31 μ L N, N-diisopropylethylamine was added, after which the above acid chloride solution was slowly added by syringe and stirred at room temperature overnight. The product of column chromatography is the compound of the formula S-I2 or R-I2. The yield is 64 to 71 percent.
When the chiral aminophenyl oxazole was S-4-methyl-2- (2-aminophenyl) oxazole, the resulting product was a compound of formula S-I2-a in 65% yield. The structure detection structure of the compound is as follows:1H NMR(600 MHz,CDCl3)δ12.61(s,1H),11.26(s,1H),11.20(s,1H),10.90(s,1H),10.84(s, 1H),10.72(s,1H),10.68(s,1H),8.62(s,1H),8.29(dd,1H),8.16(dd,1H),8.14 (dd,1H),8.02(dd,1H),7.90-7.94(m,5H),8.86(dd,1H),8.84(dd,1H),7.82(dd,1H), 7.81(dd,1H),7.72(dd,1H),7.71(dd,1H),7.69(dd,1H),7.65(dd,1H),7.35-3.38 (m,3H),7.27-7.34(m,4H),7.20(m,2H),7.16(dd,1H),7.07(dd,1H),7.04(dd,1H), 6.92(s,1H),6.89(dd,1H),6.85(s,1H),6.71(s,1H),6.65(s,1H),6.44(s,1H),6.31 (s,1H),6.29(s,1H),6.04(s,1H),4.15-4.18(m,1H),4.10-4.15(m,3H),4.00-4.07(m, 2H),3.78-3.96(m,13H),3.74(t,1H),3.66(t,1H),2.83(t,1H),2.33~2.51(m,10H), 2.21(m,2H),2.17(dd,1H),1.84(m,2H),1.11-1.34(m,50H),0.51(s,9H),0.22(d, 3H).13C NMR(151MHz,CDCl3)δ176.00,163.09,162.96,162.74,162.64,162.49, 162.36,162.26,162.10,161.42,161.35,161.11,160.90,159.97,159.47,159.22, 158.85,149.78,149.71,149.55,149.18,148.78,148.74,148.57,148.31,138.45, 138.13,137.72,137.69,137.40,137.27,137.14,133.65,133.62,133.43,133.10, 133.00,132.93,132.56,131.19,128.91,127.40,126.64,126.52,126.39,126.15, 125.84,125.69,125.66,122.60,122.46,122.26,122.18,122.03,121.92,121.62, 121.40,119.88,117.20,116.96,116.79,116.71,116.61,116.23,116.18,116.03, 115.81,115.70,115.64,113.83,99.51,99.10,98.84,98.57,98.50,98.44,97.88,75.36, 75.21,75.17,75.14,75.06,75.03,74.90,71.11,60.69,39.42,29.75,28.25,28.20, 28.17,28.12,28.09,26.79,22.75,21.15,19.69,19.61,19.53,19.49,19.45,19.34, 19.32,19.27.MS(ESI)calculated for[M+2H]2+1099.5056, found 1099.5072; the results of the detection revealed that the above compound had a correct structure.
When the chiral aminophenyl oxazole is S-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula S-I2-b in 76% yield. The structure detection structure of the compound is as follows:1H NMR(600 MHz,CDCl3)δ12.51(s,1H),11.32(s,1H),11.21(s,1H),11.10(s,1H),10.86(s, 1H),10.72(s,1H),10.69(s,1H),8.62(s,1H),8.16(dd,1H),8.15(dd,1H),8.03(dd, 1H),7.95(dd,1H),7.94(dd,1H),7.90-7.92(m,4H),7.82(dd,1H),7.81(dd,1H), 7.76(dd,1H),7.74(dd,1H),7.72(dd,1H),7.70(dd,1H),7.65(dd,1H),7.40(dd, 1H),7.35(m,3H),7.29(m,4H),7.17(dd,1H),7.19(dd,1H),7.05(m,2H),6.93(dd, 1H)6.92(s,1H),6.85(s,1H),6.73(s,1H),6.61(dd,1H),6.60(s,1H),6.51(dd,1H), 6.40(s,1H),6.33(s,1H),6.33(s,1H),6.17(s,1H),6.03(s,1H),4.17(m,1H),4.12 (m,2H),4.07(m,3H),4.00(dd,2H),3.89-3.95(m,6H),3.82(m,2H),3.77(dd,1H), 3.71(t,1H),3.65(t,1H),3.14(t,1H),2.75(t,1H),2.62(dd,1H),2.33-2.46(m,8H),2.20 (m,1H),1.09-1.36(m,50H),0.51(s,9H).13C NMR(151MHz,CDCl3)δ176.02, 163.11,162.98,162.80,162.75,162.51,162.20,161.44,160.91,160.69,160.04, 159.47,159.23,158.88,149.81,149.72,149.19,149.07,148.74,148.60,148.31, 141.03,138.50,137.97,137.76,137.67,137.44,137.29,137.15,133.66,133.45, 133.03,132.93,132.59,131.48,129.11,127.89,127.48,126.82,126.66,126.40, 126.15,125.88,125.72,125.63,125.55,122.58,122.27,122.04,121.91,121.44, 120.13,117.24,116.99,116.70,116.43,116.27,116.18,116.05,115.82,113.75,99.52, 99.10,98.80,98.43,97.97,75.37,75.24,75.19,75.11,75.03,74.87,71.92,68.80, 39.42,32.00,29.77,29.44,28.26,28.14,26.78,22.76,19.70,19.62,19.53,19.51, 19.45,19.34,19.32,19.27,14.19.MS(ESI)calculated for[M+2H]2+1130.5134, found 1130.5140; the results of the detection revealed that the above compound had a correct structure.
When the chiral aminophenyl oxazole was S-4-isopropyl-2- (2-aminophenyl) oxazole, the resulting product was a compound of formula S-I2-c in 67% yield. The structure detection structure of the compound is as follows:1H NMR(400 MHz,CDCl3)δ12.68(s,1H),11.27(s,2H),11.22(s,1H),10.90(s,1H),10.87(s, 1H),10.73(s,1H),10.69(s,1H),8.63(s,1H),8.24(d,1H),8.17(dd,1H),8.03(dd, 1H),7.90-7.93(m,4H),7.88(d,1H),7.80-7.87(m,4H),7.75(d,1H),7.71(d, 1H),7.65(d,1H),7.39(d,1H),7.38(d,1H),7.29-7.35(m,5H),7.14-7.24(m,3H), 7.04(dd,1H),7.03(dd,1H),6.91(s,1H),6.90(dd,1H),6.85(s,1H),6.73(s,1H), 6.66(s,1H),6.46(s,1H),6.31(s,1H),6.27(s,1H),6.03(s,1H),4.09-4.18(m,6H), 3.87-4.05(m,11H),3.77-3.83(m,5H),3.37(t,1H),3.65(t,1H),2.97(t,1H), 2.34-2.53(m,11H),2.22(t,2H),1.64(t,1H)0.96-1.43(m110H),0.88(s,9H),-0.07 (d,3H),-0.12(d,3H).13C NMR(101MHz,CDCl3)δ176.02,163.09,162.95,162.71, 162.51,162.32,162.27,162.22,161.43,160.89,159.88,159.49,159.26,158.88, 149.79,149.71,149.52,149.23,148.94,148.70,148.57,148.31,138.63,138.04, 137.74,137.71,137.42,137.37,137.27,137.15,133.61,133.43,133.09,133.01, 132.93,132.57,131.23,129.06,127.45,126.65,126.57,126.39,126.16,125.83, 125.69,122.60,122.46,122.26,122.17,122.01,121.92,121.56,121.43,119.74, 117.24,117.11,116.99,116.74,116.65,116.24,116.05,115.80,115.66,113.55,99.52, 99.11,98.84,98.54,98.47,98.41,97.83,75.36,75.21,75.06,74.91,71.27,67.85, 39.42,32.62,32.00,29.77,29.43,28.24,28.21,28.16,28.13,26.78,22.76,19.69, 19.61,19.56,19.53,19.45,19.34,19.28,18.04,17.21,14.19.MS(ESI)calculated for [M+2H]2+1113.5212, found 1130.5235; the results of the detection revealed that the above compound had a correct structure.
When the chiral aminophenyl oxazole is S-4-benzyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula S-I2-d in 64% yield. The structure detection structure of the compound is as follows:1H NMR(600 MHz,CDCl3)δ12.53(s,1H),11.22(s,1H),11.19(s,1H),10.98(s,1H),10.83(s, 1H),10.83(s,1H),10.72(s,1H),10.67(s,1H),8.62(s,1H),8.19(m,3H),8.01(dd, 1H),7.89-7.93(m,4H),7.79-7.83(m,4H),7.75(dd,1H),7.71(dd,1H),7.69(dd, 1H),7.64(dd,1H),7.37(dd,1H),7.35(dd,1H),7.33(dd,1H),7.27-7.31(m,3H),7.21 (dd,1H),7.19(dd,1H),7.16(dd,1H),7.05(dd,1H),7.03(dd,1H),6.91(dd,1H),6.90 (dd,1H),6.84(s,1H),6.73(s,1H),6.66(s,1H),6.43(s,1H),6.32(s,1H),6.31(s,1H), 6.28(s,1H),6.25(s,1H),6.23(dd,1H),6.20(s,1H),6.19(s,1H),6.01(s,1H),4.16(t, 1H),4.10-4.17(m3H),4.02(t,1H),3.93-3.98(m,4H),3.77-3.91(m,10H),3.64(t, 1H),3.00(t,1H),2.22-2.52(m,8H),1.95(t,1H),1.83-1.87(dd,2H),1.15-1.35(m, 73H),0.50(s,9H).13C NMR(151MHz,CDCl3)δ176.01,163.09,162.96,162.66, 162.62,162.48,162.33,162.27,162.13,161.91,161.43,160.90,160.87,159.91, 159.47,159.23,158.88,149.79,149.71,149.20,149.02,148.63,148.55,148.31, 138.68,138.11,137.71,137.43,137.42,137.36,137.27,137.14,136.91,133.69, 133.64,133.61,133.44,133.11,133.02,132.94,132.61,131.38,129.06,128.21, 127.40,127.34,126.64,126.44,126.38,126.13,125.85,125.71,125.68,125.16, 122.64,122.48,122.26,122.18,122.01,121.98,121.92,121.60,121.41,119.86, 117.30,117.19,116.96,116.72,116.63,116.52,116.26,116.22,116.19,116.06, 115.80,115.70,115.63,113.55,99.52,99.49,99.24,98.82,98.46,98.40,98.05,75.38, 75.36,75.19,75.05,75.02,74.92,69.35,67.08,42.16,39.42,29.77,29.39,28.26, 28.25,28.20,28.16,28.13,28.09,27.29,26.78,22.76,19.70,19.68,19.65,19.54, 19.52,19.51,19.48,19.45,19.42,19.37,19.33,19.31,19.27,19.26,14.18,0.06.MS (ESI)calculated for[M+2H]2+1137.5212, found 1137.5234; the results of the detection revealed that the above compound had a correct structure.
When the chiral aminophenyl oxazole is R-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula R-I2 in 76% yield. The structure detection structure of the compound is as follows:1H NMR(600 MHz,CDCl3)δ12.51(s,1H),11.33(s,1H),11.21(s,1H),11.10(s,1H),10.86(s, 1H),10.72(s,1H),10.69(s,1H),8.62(s,1H),8.16(dd,1H),8.15(dd,1H),8.03(dd, 1H),8.14(dd,1H),7.96(dd,1H),7.94(dd,1H),7.90-7.92(m,4H),7.81(dd,1H), 7.81(dd,1H),7.77(dd,1H),7.75(dd,1H),7.72(dd,1H),7.70(dd,1H),7.65(dd, 1H),7.40(dd,1H),7.35(m,3H),7.29(m,4H),7.17(dd,1H),7.19(dd,1H),7.05(m, 2H),6.93(dd,1H)6.92(s,1H),6.85(s,1H),6.73(s,1H),6.61(dd,1H),6.60(s,1H), 6.51(dd,1H),6.40(s,1H),6.33(s,1H),6.33(s,1H),6.17(s,1H),6.03(s,1H),4.17 (m,1H),4.12(m,2H),4.07(m,3H),4.00(dd,2H),3.89-3.95(m,6H),3.82(m,2H), 3.76(t,1H),3.71(t,1H),3.65(t,1H),3.14(t,1H),2.75(t,1H),2.62(dd,1H), 2.33-2.46(m,8H),2.20(m,1H),1.09-1.36(m,50H),0.51(s,9H).13C NMR(151MHz,CDCl3)δ176.03,163.11,162.98,162.80,162.75,162.51,162.41,162.27,162.20,162.14,161.44,160.91,160.69,160.04,159.47,159.23,158.88,149.81,149.71,149.18,149.07,148.74,148.60,148.30,141.02,138.50,137.97,137.76,137.67,137.44,137.29,137.14,133.66,133.45,133.03,132.93,132.58,131.49,130.97,129.11,128.91,127.89,127.48,126.82,126.66,126.48,126.40,126.15,125.89,125.73,125.64,125.55,122.58,122.27,122.21,122.03,121.91,121.44,120.13,117.24,116.99,116.90,116.75,116.70,116.43,116.27,116.18,116.05,115.83,115.75,115.65,113.75,99.52,99.10,98.80,98.53,98.42,97.96,75.35,75.24,75.19,75.11,75.03,74.87,71.92,68.80,65.64,39.42,32.00,30.66,29.77,29.44,28.26,28.16,28.12,26.79,22.77,19.68,19.62,19.53,19.51,19.46,19.34,19.33,19.27,14.19,13.80.MS(ESI)calculated for[M+2H]2+1130.5134, found 1130.5148; the results of the detection revealed that the above compound had a correct structure.
Example 3
Preparation of Compounds of formula S-I3 or R-I3
The reaction formula is as follows:
the preparation process comprises the following steps:
1) dissolving 200mg L of the mixture in a 50mL two-mouth bottle under the protection of argon in 3mL of anhydrous dichloromethane, adding 5 mu L of oxalyl chloride by using an injector, stirring at room temperature for two hours, distilling under reduced pressure to remove an organic solvent, continuing vacuumizing on a vacuum pump for two hours, and dissolving in 1mL of anhydrous dichloromethane under the protection of argon for later use; the amount of substance 0.9 equivalents of 4-R-yl-2- (2-aminophenyl) oxazole was dissolved in anhydrous dichloromethane under argon in a 50mL two-necked flask and 11 μ L N, N-diisopropylethylamine was added, after which the above acid chloride solution was slowly added by syringe and stirred at room temperature overnight. Separating the product by column chromatography to obtain the compound M with the yield of 61-63 percent.
2) Mixing 150mg of compound M with 15mg of 10% palladium-carbon solid, dissolving in 5mL of ethyl acetate, and heating and stirring the solution in 1.0 MPa hydrogen overnight under the pressure of the solution; preferably, the reaction temperature is 60 ℃; and cooling the reaction solution, filtering out palladium-carbon solid after reaction through diatomite, and distilling the obtained filtrate under reduced pressure to remove the solvent to obtain yellow solid, namely the compound N. The yield is 89-95%;
3) 490mg of N is added into a 25mL two-port bottle, argon is used as protective gas, the compound is dissolved into 10mL of anhydrous dichloromethane, 10 mu L of N, N-diisopropylethylamine and 8 mu L of pivaloyl chloride are slowly added by a syringe, and stirring is carried out for 3 hours at room temperature; separating the yellow powdery product O of the product by column chromatography to obtain the compound shown as S-I3 or R-I3. The yield is 64-71%.
When the chiral aminophenyl oxazole is S-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula S-I3 in 71% yield. The structure detection structure of the compound is as follows:1H NMR(600 MHz,CDCl3)δ12.27(s,1H),10.92(s,1H),10.78(s,1H),10.77(s,1H),10.40(s, 1H),10.36(s,1H),10.25(s,1H),10.17(s,1H),10.14(s,1H),10.08(s,1H),10.06(s, 1H),10.02(s,1H),9.99(s,1H),9.96(s,1H),9.95(s,1H),9.92(s,1H),8.39(s,1H), 7.97(d,1H),7.92(d,1H),7.73-7.79(m,6H),7.68-7.71(m,5H),7.59-7.65(m,12H), 7.55(d,1H),7.50(d,1H),7.39(d,1H),7.31(d,1H),7.20(d,1H),7.18(d,1H), 7.07-7.12(m,3H),6.94-7.00(m,9H),6.92(d,1H),6.91(d,1H),6.90(d,1H),6.86(d, 1H),6.85(d,1H),6.75-6.81(7H),6.67(s,1H),6.65(s,1H),6.50(dd,1H),6.48(s, 1H),6.45(s,1H),6.41(d,1H),6.40(d,1H),6.27(dd,1H),6.06(s,1H),6.03(s,1H), 6.01(s,1H),6.00(s,1H),5.93(s,1H),5.90(s,1H),5.87(s,1H),5.79(s,1H),5.77(s, 1H),5.77(s,1H),5.74(s,1H),5.73(s,1H),5.73(s,1H),5.70(s,1H),3.95(m,2H), 3.83-3.87(m,2H),3.74-3.79(m,5H),3.63-3.71(m,16H),3.49-3.60(m,15H),3.00(t, 1H),2.52(t,1H),2.42(dd,1H),2.71-2.31(m,20H),1.25(s,104H),1.00-1.21(m, 144H),0.84-0.94(m,30H).MS(MALDI)calculated for C244H246N34O34[M+H]+4196.86, found 4196.13; the results of the detection revealed that the above compound had a correct structure.
When the chiral aminophenyl oxazole is R-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula R-I3 in 64% yield. The structure detection structure of the compound is as follows:1H NMR(600 MHz,CDCl3)δ12.27(s,1H),10.92(s,1H),10.78(s,1H),10.77(s,1H),10.40(s, 1H),10.36(s,1H),10.25(s,1H),10.17(s,1H),10.14(s,1H),10.08(s,1H),10.06(s, 1H),10.02(s,1H),9.99(s,1H),9.96(s,1H),9.95(s,1H),9.92(s,1H),8.39(s,1H), 7.97(d,1H),7.92(d,1H),7.73-7.79(m,6H),7.68-7.71(m,5H),7.59-7.65(m,12H), 7.55(d,1H),7.50(d,1H),7.39(d,1H),7.31(d,1H),7.20(d,1H),7.18(d,1H), 7.07-7.12(m,3H),6.94-7.00(m,9H),6.92(d,1H),6.91(d,1H),6.90(d,1H),6.86(d, 1H),6.85(d,1H),6.75-6.81(7H),6.67(s,1H),6.65(s,1H),6.50(dd,1H),6.48(s, 1H),6.45(s,1H),6.41(d,1H),6.40(d,1H),6.27(dd,1H),6.06(s,1H),6.03(s,1H), 6.01(s,1H),6.00(s,1H),5.93(s,1H),5.90(s,1H),5.87(s,1H),5.79(s,1H),5.77(s, 1H),5.77(s,1H),5.74(s,1H),5.73(s,1H),5.73(s,1H),5.70(s,1H),3.95(m,2H), 3.83-3.87(m,2H),3.74-3.79(m,5H),3.63-3.71(m,16H),3.49-3.60(m,15H),3.00(t, 1H),2.52(t,1H),2.42(dd,1H),2.71-2.31(m,20H),1.25(s,104H),1.00-1.21(m, 144H),0.84-0.94(m,30H).MS(MALDI)calculated for C244H246N34O34[M+H]+4196.86, found 4196.99; the results of the detection revealed that the above compound had a correct structure.
Example 4
Preparation of Compounds of formula S-II1 or R-II1
The reaction formula is as follows:
the preparation process comprises the following steps:
1) 200mg of compound I was dissolved in 5mL of anhydrous dichloromethane in a 50mL two-neck flask under argon protection, 34. mu.L of oxalyl chloride was added by a syringe, the mixture was stirred at room temperature for two hours, the organic solvent was distilled off under reduced pressure, vacuum was applied to a vacuum pump for two hours, and the mixture was dissolved in 1mL of anhydrous dichloromethane under argon protection for further use. Dissolving 4-R group-2- (2-aminophenyl) oxazole in an amount of 0.9 equivalent in anhydrous dichloromethane in a 50mL two-necked flask under the protection of argon, adding 65 mu L N of N-diisopropylethylamine, slowly adding the above acid chloride solution by using a syringe, and stirring at room temperature overnight; separating the product by column chromatography to obtain compound J; the yield is 71% -85%;
2) 200mg of Compound J was mixed with 20mg of a 10% palladium on carbon solid, and the mixture was dissolved in 10mL of ethyl acetate, and the solution was stirred overnight under heating under a hydrogen atmosphere. Filtering out the palladium-carbon solid after reaction by using kieselguhr, and distilling the obtained filtrate under reduced pressure to remove the solvent to obtain a yellow solid, namely the compound K; the yield is 91-95%;
3) 20mg of P is dissolved in 5mL of anhydrous dichloromethane in a 50mL two-neck flask under the protection of argon, 10 mu L of oxalyl chloride is added by a syringe, the mixture is stirred for two hours at room temperature, the organic solvent is removed by distillation under reduced pressure, the vacuum is continuously pumped on a vacuum pump for two hours, and the mixture is dissolved in 3mL of anhydrous dichloromethane under the protection of argon for standby. Dissolving a substance amount of 2.0 equivalents of compound K in anhydrous dichloromethane in a 50mL two-neck flask under the protection of argon, adding 21 mu L N of N-diisopropylethylamine, slowly adding the acyl chloride solution by using a syringe, and stirring at room temperature overnight; separating the product by column chromatography to obtain a compound represented by formula S-II1 or R-II 1; the yield is 41-51%.
When the chiral aminophenyl oxazole is S-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula S-II1 in 41% yield. The structure detection structure of the compound is as follows:1H NMR(600 MHz,CDCl3)δ12.35(s,2H),12.04(s,2H),11.03(s,2H),10.97(s,2H),10.81(s, 2H),8.10(dd,2H),8.09(dd,2H),8.00(d,2H),7.92(d,2H),7.80(d,2H),7.68 (d,1H),7.64(d,1H),7.56(d,1H),7.47(d,1H),7.47(s,1H),7.42(d,1H),7.33(d,1H), 7.04-7.19(m,6H),7.07(dd,2H),6.88(dd,2H),6.58(d,2H),6.54(s,2H),6.52(d,2H), 6.48(d,2H),6.43(s,2H),6.26(s,2H),6.14(s,2H),6.13(s,2H),6.11(s,2H),6.07 (s,2H),3.84-3.91(m,16H),3.73-3.79(m,6H),3.64-3.66(m,4H),3.09(t,2H),2.74 (dd,2H),2.36-2.50(m,10H),2.22-2.29(m,4H),2.12-2.15(m,2H),1.23-1.33(m, 160H).13C NMR(151MHz,CDCl3)δ162.68,162.61,162.10,162.06,161.84,161.75, 161.58,160.53,159.78,159.74,159.55,148.90,148.81,148.48,148.21,147.43, 142.52,141.18,138.61,138.02,137.75,137.03,136.68,133.72,133.44,133.18, 133.10,131.21,129.18,127.85,127.32,126.73,126.45,126.22,125.54,122.26, 121.55,121.46,121.10,120.82,119.98,119.82,119.00,116.91,116.71,116.64, 116.21,115.98,115.04,113.68,99.63,98.41,98.13,97.56,75.28,75.17,75.04,74.81, 71.85,68.76,32.00,29.85,29.77,29.68,29.40,29.32,28.35,28.29,28.24,28.21, 28.08,27.29,25.61,22.76,19.80,19.75,19.68,19.59,19.55,19.42,19.31,14.18, 1.09,0.07.MS(ESI)calculated for C164H160N22O22[M+H]2+1395.6111, found 1395.6115; the results of the detection revealed that the above compound had a correct structure.
When the chiral aminophenyl oxazole is R-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula R-II1 in 51% yield. The structure detection structure of the compound is as follows:1H NMR(400 MHz,CDCl3)δ12.35(s,2H),12.04(s,2H),11.03(s,2H),10.97(s,2H),10.81(s, 2H),8.10(dd,2H),8.09(dd,2H),8.00(d,2H),7.92(d,2H),7.80(d,2H),7.68(d,1H), 7.64(d,1H),7.56(d,1H),7.47(d,1H),7.47(s,1H),7.42(d,1H),7.33(d,1H),7.04-7.19 (m,6H),7.07(dd,2H),6.88(dd,2H),6.58(d,2H),6.54(s,2H),6.52(d,2H),6.48 (d,2H),6.43(s,2H),6.26(s,2H),6.14(s,2H),6.13(s,2H),6.11(s,2H),6.07 (s,2H),3.84-3.91(m,16H),3.73-3.79(m,6H),3.64-3.66(m,4H),3.09(t,2H),2.74 (dd,2H),2.36-2.50(m,10H),2.22-2.29(m,4H),2.12-2.15(m,2H),1.23-1.33(m, 200H).13C NMR(151MHz,CDCl3)δ163.30,163.20,163.13,163.04,162.62,162.53, 162.16,161.77,160.62,153.67,150.53,149.86,149.33,145.52,141.29,139.11, 138.98,138.45,138.23,135.45,133.93,133.92,131.79,129.64,128.73,128.09, 127.93,127.02,126.73,126.50,125.74,125.70,124.19,124.09,122.98,122.59, 122.04,121.92,120.47,117.66,117.09,116.71,116.50,115.26,100.36,99.97,99.00, 97.73,75.79,75.45,75.43,75.20,72.16,69.09,53.68,41.95,32.00,29.76,29.73, 29.43,29.39,28.38,28.36,28.30,28.24,22.76,19.53,19.51,19.46,19.43,19.40, 19.34,19.28,19.26,18.68,17.40,14.18,12.06.MS(ESI)calculated for C164H160N22O22[M+H]2+1395.6111, found 1395.6134; the results of the detection revealed that the above compound had a correct structure.
Examples 5,
Preparation of Compounds of formula S-II2 or R-II2
The reaction formula is as follows:
the preparation process comprises the following steps:
1) dissolving 200mg of compound R in 3mL of anhydrous dichloromethane in a 50mL two-neck flask under the protection of argon, adding 17 mu L of oxalyl chloride by using an injector, stirring at room temperature for two hours, removing the organic solvent by reduced pressure distillation, continuously vacuumizing on a vacuum pump for two hours, and dissolving in 1mL of anhydrous dichloromethane under the protection of argon for later use; the amount of substance 0.9 equivalents of 4-R-yl-2- (2-aminophenyl) oxazole was dissolved in anhydrous dichloromethane under argon in a 50mL two-necked flask and 35 μ L N, N-diisopropylethylamine was added, after which the above acid chloride solution was slowly added by syringe and stirred at room temperature overnight. Separating the product by column chromatography to obtain compound S; the yield is 71% -85%;
2) mixing 200mg of compound S with 20mg of 10% palladium-carbon solid, dissolving in 10mL of ethyl acetate, and heating and stirring the solution overnight under the atmospheric pressure in a hydrogen atmosphere; filtering out the palladium-carbon solid after reaction by using kieselguhr, and distilling the obtained filtrate under reduced pressure to remove the solvent to obtain a yellow solid, namely the compound T; the yield is 91-95%;
3) 20mg of P is dissolved in 10mL of anhydrous dichloromethane in a 50mL two-neck flask under the protection of argon, 10 mu L of oxalyl chloride is added by a syringe, the mixture is stirred for two hours at room temperature, the organic solvent is removed by distillation under reduced pressure, the vacuum is continuously pumped on a vacuum pump for two hours, and the mixture is dissolved in 3mL of anhydrous dichloromethane under the protection of argon for standby. Dissolving a substance amount of 2.0 equivalents of compound T in anhydrous dichloromethane in a 50mL two-neck flask under the protection of argon, adding 21 mu L N of N-diisopropylethylamine, slowly adding the acyl chloride solution by using a syringe, and stirring at room temperature overnight; separating the product by column chromatography to obtain a compound of formula S-II2 or R-II 2; the yield is 28-33%.
When the chiral aminophenyl oxazole is S-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula S-II2 in 33% yield. The structure detection structure of the compound is as follows:1H NMR(600 MHz,CDCl3)δ12.41(s,1H),11.64(s,1H),11.14(s,1H),11.01(s,1H),10.95(s, 1H),10.68(s,1H),10.60(s,1H),10.58(s,1H),10.51(s,1H),8.11(d,1H),8.06(d, 1H),8.03(d,1H),7.97(d,1H),7.96(d,1H),7.92(d,1H),7.90(d,1H),7.87(d,1H), 7.82(d,1H),7.80(d,1H),7.76(d,1H),7.74(d,1H),7.72(d,1H),7.71(d,1H),7.62 (d,1H),7.56(d,1H),7.41(d,1H),7.28-7.32(m,6H),7.19-7.24(m,10H),7.15(dd, 1H),7.09-7.12(m,3H),7.03-7.08(m,4H),7.02(s,1H),6.92(s,1H),6.89(d,1H), 6.88(d,1H),6.59(s,1H),6.57(d,1H),6.57(s,1H),6.50(s,1H),6.48(d,1H),6.47 (d,1H),6.28(s,1H),6.28(s,1H),6.15(s,1H),6.12(s,1H),6.11(s,1H),6.10(s,1H), 5.93(s,1H),4.11(m,2H),3.99-4.04(m,2H),3.84-3.92(m,20H),3.68-3.79(m,20H), 3.58(t,1H),3.08(t,1H),2.67(t,1H),2.52(dd,1H),2.33-2.44(m,19H),0.81-1.35(m, 90H).13C NMR(101MHz,CDCl3)δ162.56,162.35,161.99,161.91,161.68,161.21, 161.03,160.93,160.39,159.63,158.99,158.76,158.35,148.90,148.55,148.37, 148.31,148.20,147.57,147.31,146.66,141.81,140.94,138.28,137.73,137.42, 137.04,136.91,136.75,136.23,135.97,133.35,133.19,132.52,132.31,131.32, 128.91,127.73,127.20,126.65,126.30,125.94,125.62,125.41,125.15,122.41, 121.95,121.70,121.23,121.09,120.30,119.99,119.27,118.43,116.61,116.32, 115.38,114.62,113.53,99.34,98.48,98.22,98.07,97.82,97.61,74.88,74.70,72.29, 71.71,68.56,32.01,31.52,30.39,30.28,29.78,29.44,28.87,28.53,28.11,28.01, 27.89,27.80,22.78,21.99,21.45,19.69,19.61,19.56,19.47,19.38,19.34,19.24, 19.21,14.21,9.76.MS(MALDI)calculated for C276H274N38O38[M+H]+4729.0755, found 4729.51; the results of the detection revealed that the above compound had a correct structure.
When the chiral aminophenyl oxazole is R-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula R-II2 in 28% yield. The structure detection structure of the compound is as follows:1H NMR(600 MHz,CDCl3)δ12.41(s,1H),11.64(s,1H),11.14(s,1H),11.01(s,1H),10.95(s, 1H),10.68(s,1H),10.60(s,1H),10.58(s,1H),10.51(s,1H),8.11(d,1H),8.06(d, 1H),8.03(d,1H),7.97(d,1H),7.96(d,1H),7.92(d,1H),7.90(d,1H),7.87(d,1H), 7.82(d,1H),7.80(d,1H),7.76(d,1H),7.74(d,1H),7.72(d,1H),7.71(d,1H),7.62 (d,1H),7.56(d,1H),7.41(d,1H),7.28-7.32(m,6H),7.19-7.24(m,10H),7.15(dd, 1H),7.09-7.12(m,3H),7.03-7.08(m,4H),7.02(s,1H),6.92(s,1H),6.89(d,1H), 6.88(d,1H),6.59(s,1H),6.57(d,1H),6.57(s,1H),6.50(s,1H),6.48(d,1H),6.47 (d,1H),6.28(s,1H),6.28(s,1H),6.15(s,1H),6.12(s,1H),6.11(s,1H),6.10(s,1H), 5.93(s,1H),4.11(m,2H),3.99-4.04(m,2H),3.84-3.92(m,20H),3.68-3.79(m,20H), 3.58(t,1H),3.08(t,1H),2.67(t,1H),2.52(dd,1H),2.33-2.44(m,19H),0.81-1.35(m, 90H).13C NMR(101MHz,CDCl3)δ162.56,162.35,161.99,161.91,161.68,161.21, 161.03,160.93,160.39,159.63,158.99,158.76,158.35,148.90,148.55,148.37, 148.31,148.20,147.57,147.31,146.66,141.81,140.94,138.28,137.73,137.42, 137.04,136.91,136.75,136.23,135.97,133.35,133.19,132.52,132.31,131.32, 128.91,127.73,127.20,126.65,126.30,125.94,125.62,125.41,125.15,122.41, 121.95,121.70,121.23,121.09,120.30,119.99,119.27,118.43,116.61,116.32, 115.38,114.62,113.53,99.34,98.48,98.22,98.07,97.82,97.61,74.88,74.70,72.29, 71.71,68.56,32.01,31.52,30.39,30.28,29.78,29.44,28.87,28.53,28.11,28.01, 27.89,27.80,22.78,21.99,21.45,19.69,19.61,19.56,19.47,19.38,19.34,19.24, 19.21,14.21,9.76.MS(ESI)calculated for C276H274N38O38[M+Na]+4751.0574, found 4750.69; from the results of the detection, the above-mentionedThe compound has correct structure.
Example 6
Preparation of Compounds of formula S-II3 or R-II3
The reaction formula is as follows:
the preparation process comprises the following steps:
1) dissolving 200mg L of the mixture in a 50mL two-mouth bottle under the protection of argon in 3mL of anhydrous dichloromethane, adding 5 mu L of oxalyl chloride by using an injector, stirring at room temperature for two hours, distilling under reduced pressure to remove an organic solvent, continuing vacuumizing on a vacuum pump for two hours, and dissolving in 1mL of anhydrous dichloromethane under the protection of argon for later use; the amount of substance 0.9 equivalents of 4-R-yl-2- (2-aminophenyl) oxazole was dissolved in anhydrous dichloromethane under argon in a 50mL two-necked flask and 11 μ L N, N-diisopropylethylamine was added, after which the above acid chloride solution was slowly added by syringe and stirred at room temperature overnight. Separating the product by column chromatography to obtain compound M; the yield is 61-63%;
2) mixing 150mg of compound M with 15mg of 10% palladium-carbon solid, dissolving in 5mL of ethyl acetate, and heating and stirring the solution in 1.0 MPa hydrogen overnight under the pressure of the solution; preferably, the reaction temperature is 60 ℃; then cooling the reaction solution, filtering out palladium-carbon solid after reaction through diatomite, and distilling the obtained filtrate under reduced pressure to remove the solvent, wherein the obtained yellow solid is the compound N; the yield is 89-95%;
3) dissolving 10mg of P in 10mL of anhydrous dichloromethane in a 50mL two-mouth bottle under the protection of argon, adding 5 mu L of oxalyl chloride by using an injector, stirring at room temperature for two hours, distilling under reduced pressure to remove an organic solvent, continuously vacuumizing on a vacuum pump for two hours, and dissolving in 3mL of anhydrous dichloromethane under the protection of argon for later use; dissolving a compound N with the amount of 2.0 equivalents in anhydrous dichloromethane in a 50mL two-neck flask under the protection of argon, adding 10 mu L N of N-diisopropylethylamine, slowly adding the acyl chloride solution by using a syringe, and stirring at room temperature overnight; separating the product by column chromatography to obtain a compound of formula S-II3 or R-II 3; the yield is 19-25%.
When the chiral aminophenyl oxazole is S-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula S-II3 in 25% yield. The structure detection structure of the compound is as follows:1H NMR(400 MHz,CDCl3)δ12.27(s,1H),10.92(s,1H),10.78(s,1H),10.76(s,1H),10.40(s, 1H),10.36(s,1H),10.25(s,1H),10.17(s,1H),10.14(s,1H),10.08(s,1H),10.06(s, 1H),10.02(s,1H),9.99(s,1H),9.96(s,1H),9.95(s,1H),9.92(s,1H),8.39(s,1H), 7.97(d,1H),7.92(d,1H),7.59-7.79(m,25H),7.55(d,1H),7.49(d,1H),7.39(d,1H), 7.30(d,1H),7.17-7.21(m,3H),7.06-7.13(m,4H),6.93-7.02(m,12H),6.91(s,1H), 6.91(s,1H),6.89(d,1H),6.86(s,1H),6.75-6.84(m,8H),6.70(s,1H),6.65(s,1H), 6.51(d,1H),6.48(s,1H),6.45(s,1H),6.42(s,1H),6.40(d,1H),6.38(d,1H),6.06 (s,1H),6.03(s,1H),6.02(s,1H),6.00(s,1H),5.93(s,1H),5.90(s,1H),5.87(s,1H), 5.78(s,1H),5.77(s,1H),5.77(s,1H),5.74(s,1H),5.73(s,1H),5.72(s,1H),5.70(s, 1H),4.30(m,1H),3.94-3.98(m,2H),3.45-3.88(m,43H),3.37-.42(m,2H),3.00(dd, 1H),2.42(dd,1H),2.16-2.33(m,21H),2.11(dd,1H),1.39-1.49(m,6H),1.00-1.28 (m,222H),0.83-0.89(m,13H).MS(MALDI)calculated forC500H500N70O70[M+H]+8604.7795, found 8604.71; the results of the detection revealed that the above compound had a correct structure.
When the chiral aminophenyl oxazole is R-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula R-II3 in 19% yield. The structure detection structure of the compound is as follows:1H NMR(400 MHz,CDCl3)δ12.27(s,1H),10.92(s,1H),10.78(s,1H),10.76(s,1H),10.40(s, 1H),10.36(s,1H),10.25(s,1H),10.17(s,1H),10.14(s,1H),10.08(s,1H),10.06(s, 1H),10.02(s,1H),9.99(s,1H),9.96(s,1H),9.95(s,1H),9.92(s,1H),8.39(s,1H), 7.97(d,1H),7.92(d,1H),7.59-7.79(m,25H),7.55(d,1H),7.49(d,1H),7.39(d,1H), 7.30(d,1H),7.17-7.21(m,3H),7.06-7.13(m,4H),6.93-7.02(m,12H),6.91(s,1H), 6.91(s,1H),6.89(d,1H),6.86(s,1H),6.75-6.84(m,8H),6.70(s,1H),6.65(s,1H), 6.51(d,1H),6.48(s,1H),6.45(s,1H),6.42(s,1H),6.40(d,1H),6.38(d,1H),6.06 (s,1H),6.03(s,1H),6.02(s,1H),6.00(s,1H),5.93(s,1H),5.90(s,1H),5.87(s,1H), 5.78(s,1H),5.77(s,1H),5.77(s,1H),5.74(s,1H),5.73(s,1H),5.72(s,1H),5.70(s, 1H),4.30(m,1H),3.94-3.98(m,2H),3.45-3.88(m,43H),3.37-.42(m,2H),3.00(dd, 1H),2.42(dd,1H),2.16-2.33(m,21H),2.11(dd,1H),1.39-1.49(m,6H),1.00-1.28 (m,222H),0.83-0.89(m,13H).MS(MALDI)calculated forC500H500N70O70[M+H]+8604.7795, found 8604.63; the results of the detection revealed that the above compound had a correct structure.
Example 7,
The compounds prepared in examples 1 to 6 were subjected to measurement of ultraviolet-visible absorption spectrum, fluorescence spectrum, circular dichroism spectrum and circular polarized light emission spectrum as shown in table 1 using methylene chloride as a solvent, and circular dichroism spectrum and circular polarized light emission spectrum as shown in fig. 1 to 18.
As can be seen from table 1 and fig. 13 to 15, fig. 16 to 18, the g values of the circularly polarized luminescence and the quantum yields of the compounds prepared according to the present invention increased as the chain length of the compounds increased.
TABLE 1 optical Properties of the Compounds prepared in examples 1-6
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. All obvious changes and modifications which are obvious to the technical scheme of the invention are covered by the protection scope of the invention.
Claims (9)
1. A chiral fluorescent compound based on a quinoline amide foldate, which is characterized in that: the structural general formula of the compound is shown as the following formula I or formula II,
in the formula I or formula II, R1Is an isobutyl group; r2Is methyl, phenyl, isobutyl, benzyl or isopropyl; r3Is tert-butyl and n is 4, 8 or 16.
2. The chiral fluorescent compound based on a quinoline amide fold according to claim 1, characterized in that:
the compound comprises an S enantiomer and an R enantiomer; wherein,
the structural formula of the S-type enantiomer is shown as the following formula S-I or formula S-II,
the structural formula of the R enantiomer is shown as the following formula R-I or R-II,
formula S-I, formula S-II, formula R-I or formula R-II wherein R1Is an isobutyl group; r2Is methyl, phenyl, isobutyl, benzyl or isopropyl; r3Is tert-butyl and n is 4, 8 or 16.
3. A method for preparing a chiral fluorescent compound based on a quinoline amide foldate, wherein the compound is shown as formula I in claim 1, and the method comprises the following steps:
1) under the protection of argon, 4-substituted chiral 2- (2-aminophenyl) oxazole is dissolved in anhydrous dichloromethane, and N, N-diisopropylethylamine is added as alkali to obtain a solution a; dissolving carboxylic acid of the 4-isobutoxy-8-amino-2-carboxyl quinoline amide polymer in anhydrous dichloromethane to obtain a solution b; mixing the solution a and the solution b and stirring to obtain a single chiral quinoline amide polymer;
2) dissolving the single-chiral quinoline amide polymer obtained in the step 1) and 10% palladium-carbon in ethyl acetate in a hydrogen atmosphere, and heating and stirring to obtain amine of the single-chiral quinoline amide polymer;
3) under the protection of argon, taking anhydrous dichloromethane as a solvent, taking N, N-diisopropylethylamine as a base, and stirring the amine of the single chiral quinoline amide polymer obtained in the step 2) and pivaloyl chloride at room temperature for 2-4 hours to obtain a compound shown in a formula I;
in the step 1), the structural formula of the 4-substituted chiral 2- (2-aminophenyl) oxazole is as follows:
wherein R is methyl, phenyl, isobutyl, benzyl or isopropyl;
in step 1), the carboxylic acid of the 4-isobutoxy-8-amino-2-carboxyquinoline amide multimer has the following structural formula:
in the step 1), the structural formula of the single chiral quinoline amide polymer is as follows:
wherein n is 4, 8, 16; r is methyl, phenyl, isobutyl, benzyl or isopropyl;
in the step 2), the amine of the chiral quinoline amide polymer has the following structural formula:
wherein R is methyl, phenyl, isobutyl, benzyl or isopropyl.
4. The method for preparing a chiral fluorescent compound based on a quinoline amide fold according to claim 3,
in the step 1), the ratio of the amount of the carboxylic acid of the N, N-diisopropylethylamine and 4-isobutoxy-8-amino-2-carboxyl quinoline amide polymer to the amount of the 4-substituted chiral 2- (2-aminophenyl) oxazole is 2-100: 1: 0.85-10;
in the step 2), the pressure of hydrogen is 0.8-1.5 MPa, the heating temperature is 40-60 ℃, the heating and stirring time is 6-15 hours, and the mass ratio of the single chiral quinoline amide polymer to 10% palladium-carbon is 10: 1-3;
in the step 3), the ratio of the amount of the pivaloyl chloride to the amount of the amine of the single chiral quinoline amide polymer is 1-500: 1.
5. A method for preparing a chiral fluorescent compound based on a quinoline amide foldate, wherein the compound is shown as formula I in claim 1, and the method comprises the following steps:
1) under the protection of argon, anhydrous dichloromethane is used as a solvent, N, N-diisopropylethylamine is used as a base, and the amine of the 4-isobutoxy-8-amino-2-carboxyl quinoline amide polymer and pivaloyl chloride are stirred at room temperature for 2-4 hours to obtain a fluorescence product pivaloyl quinoline amide polymer;
2) dissolving the pivaloyl quinoline amide polymer obtained in the step 1) in a mixed solvent of tetrahydrofuran and methanol, dissolving NaOH in deionized water, adding the dissolved NaOH, and heating and stirring for 1-4 h to obtain carboxylic acid of the pivaloyl quinoline amide polymer;
3) under the protection of argon, dissolving the carboxylic acid of the pivaloyl quinoline amide polymer obtained in the step 2) in anhydrous dichloromethane, adding oxalyl chloride, and stirring at room temperature to obtain acyl chloride of the pivaloyl quinoline amide polymer;
4) under the protection of argon, 4-substituted chiral 2- (2-aminophenyl) oxazole is dissolved in anhydrous dichloromethane, and N, N-diisopropylethylamine is added to obtain a solution c; dissolving acyl chloride of the pivaloyl quinoline amide polymer obtained in the step 3) in anhydrous dichloromethane to obtain a solution d, and mixing the solutions c and d to obtain a compound shown in the formula I;
in step 1), the amine of the 4-isobutoxy-8-amino-2-carboxyquinoline amide multimer has the following structural formula:
in the step 1), the structural formula of the pivaloyl quinoline amide polymer is as follows:
in step 2), the structural formula of the carboxylic acid of the pivaloyl quinoline amide polymer is as follows:
in the step 3), the structural formula of the acyl chloride of the pivaloyl quinoline amide polymer is as follows:
in the step 4), the structural formula of the 4-substituted chiral 2- (2-aminophenyl) oxazole is as follows:
wherein R is methyl, phenyl, isobutyl, benzyl or isopropyl.
6. The method of claim 5, wherein the chiral fluorescent compound is selected from the group consisting of:
in the step 1), the mass ratio of the amine of the N, N-diisopropylethylamine and 4-isobutoxy-8-amino-2-carboxyl quinoline amide polymer to the pivaloyl chloride is 2-100: 1: 0.85-10;
in the step 2), the mass ratio of tetrahydrofuran, methanol and water is 5-100: 1-100: 0.1-50; the mass ratio of the pivaloyl quinoline amide polymer to the sodium hydroxide is 1: 10-1: 20;
in the step 3), the mass ratio of the carboxylic acid to the oxalyl chloride of the pivaloyl quinoline amide polymer is 1: 2-100;
in the step 4), the ratio of the acyl chloride of the pivaloyl quinoline amide polymer to the substance of 4-substituted chiral 2- (2-aminophenyl) oxazole is 1: 0.85-1.2.
7. A method for preparing a chiral fluorescent compound based on a quinoline amide foldate, wherein the compound is shown as formula II in claim 1, and the method comprises the following steps:
1) under the protection of argon, dissolving 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid in anhydrous dichloromethane, adding oxalyl chloride, and stirring at room temperature to obtain 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid chloride;
2) under the protection of argon, dissolving amine of the chiral quinoline amide polymer in anhydrous dichloromethane, and adding N, N-diisopropylethylamine to obtain a solution e; dissolving the 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid chloride obtained in the step 1) in anhydrous dichloromethane to obtain a solution f; mixing the solution e and the solution f, and stirring to obtain a compound shown in a formula II;
in the step 2), the amine of the chiral quinoline amide polymer has the following structural formula:
wherein R is methyl, phenyl, isobutyl, benzyl or isopropyl.
8. The method for preparing a chiral fluorescent compound based on a quinoline amide fold according to claim 7,
in the step 1), the mass ratio of the 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid to oxalyl chloride is 1: 5-1000;
in the step 2), the mass ratio of the 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid chloride, N-diisopropylethylamine and the 4-substituted chiral 2- (2-aminophenyl) oxazole is 1: 5-1000: 2-10.
9. The use of a quinoline amide fold-based chiral fluorescent compound according to any one of claims 1 to 2 in the preparation of chiral organic light-emitting materials, in the preparation of chiral fluorescent probes.
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