CN114075136B - Water-soluble three-fork chiral molecule containing azobenzene pyridine, and preparation method and application thereof - Google Patents
Water-soluble three-fork chiral molecule containing azobenzene pyridine, and preparation method and application thereof Download PDFInfo
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 62
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000001338 self-assembly Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000002983 circular dichroism Methods 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 22
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 21
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 14
- 229910001510 metal chloride Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001514 detection method Methods 0.000 claims description 12
- 238000002390 rotary evaporation Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 229940125904 compound 1 Drugs 0.000 claims description 10
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 8
- 238000010898 silica gel chromatography Methods 0.000 claims description 8
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 7
- GPIQOFWTZXXOOV-UHFFFAOYSA-N 2-chloro-4,6-dimethoxy-1,3,5-triazine Chemical compound COC1=NC(Cl)=NC(OC)=N1 GPIQOFWTZXXOOV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 229940125782 compound 2 Drugs 0.000 claims description 6
- 229940125898 compound 5 Drugs 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 229940126214 compound 3 Drugs 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000000779 smoke Substances 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 abstract description 3
- 229940125773 compound 10 Drugs 0.000 description 29
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 29
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 26
- 229940126543 compound 14 Drugs 0.000 description 26
- 238000001553 co-assembly Methods 0.000 description 21
- 239000002184 metal Substances 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 19
- 229910021645 metal ion Inorganic materials 0.000 description 19
- 230000003321 amplification Effects 0.000 description 16
- 238000003199 nucleic acid amplification method Methods 0.000 description 16
- 238000001142 circular dichroism spectrum Methods 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 230000012447 hatching Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 2
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 229940125797 compound 12 Drugs 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/76—Nitrogen atoms to which a second hetero atom is attached
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses a water-soluble three-fork chiral molecule containing azobenzene pyridine, which has the following general formula:wherein, represents R configuration or S configuration. The invention also provides application of the water-soluble trigeminal chiral molecule containing azobenzene pyridine in preparation of chiral self-assembly body. The water-soluble three-fork chiral molecule containing the azobenzene pyridine prepared by the invention has the advantages of water solubility, novel target molecule, stable property, convenient access and simple and easily controlled synthesis conditions by reasonably designing the molecule, thereby providing a reference for the design and synthesis of the water-soluble molecule containing the azobenzene pyridine.
Description
Technical Field
The invention belongs to the technical field of chiral compound preparation, and particularly relates to a water-soluble trigeminal chiral molecule containing azobenzene pyridine, and a preparation method and application thereof.
Background
Chiral is common in biology and nature, and exists from molecular level, nano-helical structure, macroscopic system to universe. Chirality is very important for living beings, and for some chiral drugs, one enantiomer is safe and effective, while the other enantiomer is ineffective or even toxic, so molecular chirality has been considered as a key factor in the development of biological materials. In contrast to molecular chirality, research on supramolecular chiral assembly can lead people to further and deeper understanding of living bodies.
Circular dichroism is an optical spectrum used for chiral detection, but not all chiral compounds can be used for chiral detection, and when the ultraviolet absorption of the chiral compounds is below 250nm or the polarizing capability is weak, the circular dichroism cannot detect the chirality, namely no circular dichroism signal is generated (Huang Feihe. A water-soluble column arene chiral amplifier, a preparation method thereof and application thereof [ P ]. Chinese patent No. 110407694A,2019-11-05 ]. It is therefore very interesting and challenging to achieve chiral amplification by co-assembly of chiral molecules with achiral substances so that circular dichroism signals can be detected.
The water-soluble three-fork chiral molecule has wide application prospect in supermolecule self-assembly, and the novel three-fork chiral molecule modified by the azobenzene pyridine group has good water solubility, and can be subjected to complexation coordination co-assembly with metal ions, so that the obtained chiral co-assembly has good chiral amplification effect, and the preparation of the novel water-soluble three-fork chiral molecule containing the azobenzene pyridine and the co-assembly chiral amplification application research of the metal ions are developed through reasonable molecular design.
Disclosure of Invention
The first object of the invention is to provide a novel water-soluble trigeminal chiral molecule containing azobenzene pyridine.
The second object of the invention is to provide a preparation method of the water-soluble three-fork chiral molecule containing azobenzene pyridine.
The third object of the invention is to provide an application of the water-soluble three-fork chiral molecule containing azobenzene pyridine in preparing chiral self-assembly body.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a water-soluble trigeminal chiral molecule containing azobenzene pyridine, which has a general formula shown as follows:
wherein, represents R configuration or S configuration.
The second aspect of the invention provides a preparation method of the water-soluble three-fork chiral molecule containing azobenzene pyridine, which comprises the following steps:
wherein, represents R configuration or S configuration;
firstly, dissolving a chiral compound 1 and a chiral compound 2 in acetonitrile solution at room temperature, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDCI) and 4-Dimethylaminopyridine (DMAP), stirring for 12-24 hours under the condition of room temperature and argon atmosphere, removing the solvent by rotary evaporation, and separating by silica gel column chromatography to obtain a compound 3;
the molar ratio of the compound 1 to the compound 2 is 1 (0.8-1.2) (preferably 1:1), the molar ratio of the compound 1 to the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is 1 (1.2-3.5), and the molar ratio of the compound 1 to the 4-dimethylaminopyridine is 1 (0.1-0.2);
step two, adding the compound 3 into dichloromethane at room temperature, slowly dripping excessive trifluoroacetic acid, stirring for 12-24 hours in an air atmosphere, slowly dripping triethylamine into the reaction liquid until no smoke is generated and white precipitation is generated, extracting a product with dichloromethane, washing with saturated saline water, drying with anhydrous sodium sulfate, and removing a solvent by rotary evaporation to obtain a compound 4;
thirdly, dissolving the compound 4 and the compound 5 in N, N-dimethylformamide, adding 2-chloro-4, 6-dimethoxy-1, 3, 5-triazine (CDMT), carrying out ultrasonic treatment until the solution becomes clear, adding N-methylmorpholine (NMM) under the condition of 0 ℃, stirring for 3-8 min, gradually heating to 85-95 ℃, stirring and refluxing for 12-24 h under the argon atmosphere, removing the solvent by rotary evaporation, and separating by silica gel column chromatography to obtain the water-soluble trigeminal chiral molecule containing the azobenzene pyridine;
the mol ratio of the compound 4 to the compound 5 is 1 (3-6) (preferably 1:4); the molar ratio of the compound 4 to the 2-chloro-4, 6-dimethoxy-1, 3, 5-triazine is 1 (2-4) (preferably 1:3); the molar ratio of the compound 4 to the N-methylmorpholine is 1 (5-7) (preferably 1:6).
The chiral compound 1 has a configuration of R configuration or S configuration.
The third aspect of the invention provides an application of the water-soluble three-fork chiral molecule containing the azobenzene pyridine in preparing chiral self-assembly bodies. The method for detecting chiral signals by circular dichroism can be realized by utilizing the common assembly of the water-soluble trigeminal chiral molecules containing the azobenzene pyridine and metal ions, and the simple and rapid chiral amplification effect is realized.
The pyridine group in the water-soluble three-fork chiral molecule containing the azobenzene pyridine has a certain coordination function with metal ions to generate chiral coordination complex, the chiral coordination complex is further orderly chiral arranged to form a chiral self-assembly body, and the chiral amplification effect of the chiral self-assembly body can enhance a circular dichroism signal, so that the chiral self-assembly body can be detected to the circular dichroism signal.
The application comprises the following steps:
firstly, preparing water-soluble three-fork chiral molecules containing azobenzene pyridine into an aqueous solution, and performing circular dichroism detection on the aqueous solution, wherein the chirality of the obtained aqueous solution cannot be detected by the circular dichroism, and the signal detected by the circular dichroism is zero;
a second step of adding an aqueous solution of metal chloride selected from NaCl and CuCl into the aqueous solution of the first step and uniformly mixing 2 Or CoCl 2 The method comprises the steps of carrying out a first treatment on the surface of the Standing in dark for 5-10 days to form a chiral self-assembly body, wherein the molar ratio of the water-soluble trigeminal chiral molecule containing azobenzene pyridine to the metal chloride is 1 (8-15); the solution was subjected to circular dichroism detection, and the chirality of the obtained solution was effectively amplified, and a strong signal was detected by circular dichroism.
The concentration of the water-soluble water solution containing the three-fork chiral molecules of the azobenzene pyridine is 0.02-0.04 mmol/L, preferably 0.03mmol/L.
The concentration of the metal chloride solution is 0.05 to 0.15mol/L, preferably 0.1mol/L.
The molar ratio of the water-soluble trigeminal chiral molecule containing the azobenzene pyridine to the metal chloride is 1:10.
By adopting the technical scheme, the invention has the following advantages and beneficial effects:
in order to realize chiral induction and amplification of supermolecules, the azobenzene pyridine group is introduced into the trifurcate molecules, so that the azobenzene pyridine group can play a pi-pi stacking role in supermolecule assembly, pyridine can be co-assembled with the supermolecules through metal coordination with special metal ions, and in addition, the effect of amide hydrogen bonds can promote supermolecule assembly. The other end of the azobenzene pyridine is covalently modified with a hydrophilic glycol chain, so that the whole molecule becomes a typical amphipathic structure and has water solubility. The characteristic drives the target molecule to perform supermolecule co-assembly with the metal ion in the aqueous solution to realize supermolecule chiral amplification, so that the circular dichroism signal can be effectively enhanced, and the circular dichroism signal can be detected. The reasonable molecular design ensures that the chiral trigeminal molecule of the target compound has water solubility, and can be assembled together with special metal ions to realize the amplification of supermolecule chirality, thereby greatly improving the detection limit of circular dichroism and realizing the real-time detection of chirality.
The water-soluble three-fork chiral molecule containing the azobenzene pyridine prepared by the invention has the advantages of water solubility, novel target molecule, stable property, convenient access and simple and easily controlled synthesis conditions by reasonably designing the molecule, thereby providing a reference for the design and synthesis of the water-soluble molecule containing the azobenzene pyridine.
Drawings
FIG. 1 is a diagram of compound 10 prepared in example 1 of the present invention 1 H-NMR chart.
FIG. 2 is a schematic view of ultraviolet absorption spectrum of compound 10 prepared in example 1 of the present invention.
FIG. 3 is a schematic diagram showing a tan clear aqueous picture of compound 10 prepared in example 1 of the present invention.
FIG. 4 is a schematic representation of the configurational circular dichroism spectrum signal of compound 10 prepared in example 1 of the present invention.
FIG. 5 is a nanotopography of the chiral self-assembly of compound 10 and its metal coordinates prepared in example 1 of the present invention.
FIG. 6 is a circular dichromatic signal diagram of chiral self-assembled hatching fluid formed after the compound 10 prepared in example 1 of the present invention and its metal co-assembly.
FIG. 7 is a photograph of compound 14 prepared in example 2 of the present invention 1 H-NMR chart.
FIG. 8 is a schematic view of ultraviolet absorption spectrum of compound 14 prepared in example 2 of the present invention.
FIG. 9 is a schematic diagram showing a tan clear aqueous picture of compound 14 prepared in example 2 of the present invention.
FIG. 10 is a schematic representation of the configurational circular dichroism spectrum signal of compound 14 prepared in example 2 of the present invention.
FIG. 11 is a nanotopography of chiral self-assemblies formed after co-assembly of compound 14 and its metal prepared in example 2 of the present invention.
FIG. 12 is a circular dichroism spectrum of chiral self-assembled hatching fluid formed after the compound 14 prepared in example 2 of the present invention and metal thereof are co-assembled.
FIG. 13 is a schematic view of ultraviolet absorption spectrum of Compound II of comparative example 1 of the present invention.
FIG. 14 is a circular dichroism spectrum of chiral self-assembled hatching fluid formed after the compound II and the metal thereof of the comparative example 1 of the present invention are co-assembled.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
Example 1
The preparation method of the water-soluble three-fork chiral molecule containing the azobenzene pyridine comprises the following steps:
compound 7 (2.61 g,2.94 mmol) (configuration R), compound 2 (1.53 g,2.94 mmol), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (845 mg,4.41 mmol), 4-dimethylaminopyridine (45 mg,0.37 mmol) were placed in a 50ml flask at room temperature, and 20ml acetonitrile was added to dissolve the whole. After the reaction was completed, the solvent was removed by rotary evaporation, and 3.88g of yellow oily liquid compound 8 was separated by silica gel column chromatography (ethyl acetate/methanol, v1/v2=50/1).
Compound 8 (4.2 g,3.22 mmol) was placed in a 50ml flask containing 20ml of dichloromethane at room temperature and trifluoroacetic acid (9.6 ml,128.7 mmol) was slowly added dropwise to the reaction mixture. The reaction was stirred in air for 18 hours, triethylamine was slowly added dropwise to the reaction mixture until no smoke was generated and white precipitate was formed, the product was extracted with methylene chloride, washed 3 times with saturated brine, and dried over anhydrous sodium sulfate. The solvent was removed by rotary evaporation to give 3.64g of Compound 9 as a yellow liquid.
Compound 9 (1.19 g,1 mmol) and Compound 5 (0.91 g,4 mmol) were dissolved in 50ml of N, N-dimethylformamide, 2-chloro-4, 6-dimethoxy-1, 3, 5-triazine (0.53 g,3 mmol) was added, after sonication (25 ℃ C., 100W) until the solution became clear, N-methylmorpholine (0.61 g,6 mmol) was added at 0 ℃ C., stirring was continued for 5min, the temperature was gradually raised to 90 ℃ C., stirring was continued under reflux for 24h under argon atmosphere, the solvent was removed by rotary evaporation, and silica gel column chromatography (dichloromethane/methanol, v1/v2=40/1) was separated to give 1.42g of reddish brown solid compound 10 in 88% yield.
The specific synthetic route is as follows:
FIG. 1 is a diagram of compound 10 prepared in example 1 of the present invention 1 An H-NMR chart of the sample, 1 H NMR(400MHz,DMSO-d 6 )δ10.61(s,2H),8.88(d,J＝6.1Hz,4H),8.80(d,J＝7.4Hz,1H),8.25(d,J＝8.5Hz,4H),8.11(d,J＝8.5Hz,4H),7.96(s,4H),7.83(dd,J＝6.7,5.1Hz,8H),7.58(s,1H),7.32–7.21(m,6H),7.18(d,J＝6.9Hz,1H),7.11(s,2H),4.70(ddd,J＝9.4,8.1,6.3Hz,1H),4.54–4.42(m,2H),4.35(dt,J＝8.5,4.3Hz,2H),4.12–4.06(m,4H),4.03(d,J＝5.1Hz,2H),3.76–3.70(m,4H),3.67–3.63(m,2H),3.61–3.46(m,32H),3.41–3.38(m,6H),3.21(d,J＝5.4Hz,9H)。
FIG. 2 is a schematic view of the ultraviolet absorption spectrum of the compound 10 prepared in example 1 of the present invention, which has a main ultraviolet absorption maximum wavelength of 300nm. 24mg of compound 10 was dissolved in 3mL of water to give a brown-yellow clear aqueous solution at a concentration of 5mM, indicating that the chiral trigeminal molecule synthesized according to the present invention has good water solubility. FIG. 3 is a schematic diagram showing a tan clear aqueous picture of compound 10 prepared in example 1 of the present invention. Circular dichroism spectrum test is carried out on the aqueous solution (5 mM) of the compound 10 under the condition of high concentration, and the spectrum result shows that the compound solution shows a remarkable negative circular dichroism signal at the absorption wavelength of 300nm, which indicates that the compound 10 is chiral molecules in R configuration. FIG. 4 is a schematic representation of the configurational circular dichroism spectrum signal of compound 10 prepared in example 1 of the present invention.
Use of the water-soluble, azo-benzene pyridine-containing, trigeminal chiral molecule in the preparation of chiral self-assemblies, the use comprising the steps of:
firstly, preparing a compound 10 into an aqueous solution with the concentration of 0.03mmol/L, and performing circular dichroism detection on the low-concentration aqueous solution, wherein the chirality of the obtained aqueous solution cannot be detected by the circular dichroism, and the signal detected by the circular dichroism is zero;
second, four parts of an aqueous solution (3 mL,0.03 mmol/L) of Compound 10 was prepared at room temperature, and metal chlorides (NaCl, cuCl) were added thereto, respectively 2 、CoCl 2 Or NiCl 2 ) The water solution is 9 mu L in dosage and 0.1mol/L in concentration, the mixed solution is uniformly shaken, kept stand and hatched for 7 days in a dark place, in the water solution, the compound 10 and the metal ions are co-assembled through metal coordination, the co-assembled body is further subjected to super molecular assembly through non-covalent bond action to form a chiral self-assembled body, and the molar ratio of the compound 10 to the metal chloride is 1:10; the solution was subjected to circular dichroism detection, and the chirality of the obtained solution was effectively amplified, and a strong signal was detected by circular dichroism.
The nanostructure of the compound 10 and chiral self-assembly is shown in fig. 5, and fig. 5 is a nanotopography of the compound 10 and the chiral self-assembly with metal coordination prepared in example 1 of the present invention. The R-configuration compound 10 can be assembled into coil-like morphology in water, and the morphology of chiral self-assembly formed after co-assembly with metal can be changed, which indicates that the interaction and supermolecule assembly of metal ions and the compound 10 in aqueous solution do occur, a new supermolecule assembly is formed, and the morphology is different due to the difference of metal ions. Compound 10 and Co in aqueous solution 2+ Metal ion coordination co-assembly to form flaky film morphology like pine needle, and Na + Forming a seedling-like fibrous morphology, and Cu 2+ Forming the shape of the dendritic and regular arrangement of the petal-shaped particles and Ni 2+ Irregular aggregates are formed. This means that the chiral amplification effect of the supermolecule produced by the coordinated co-assembly of the compound 10 and the metal ion will vary from morphology to morphology.
FIG. 6 is a diagram showing the circular dichroism spectrum of a chiral self-assembled hatching fluid formed after co-assembling of compound 10 and metal thereof prepared in example 1 of the present invention, wherein an aqueous solution of compound 10 has no circular dichroism spectrum, compound 10 and metal Ni 2+ Chiral self-assembly solution formed by ion mixing has no circular dichromatic signal, which indicates that the metal Ni 2+ The introduction of ions is detrimental to the chiral amplification of the co-assembly, but with Na + 、Cu 2+ And Co 2+ After the chiral self-assembly body is formed by ion coordination co-assembly, a strong signal with a circular dichroism spectrum showing negative chirality can be obtained through supermolecule chiral amplification, and the circular dichroism signals of the chiral co-assembly body have different intensities due to different morphologies of the co-assembly body. It is shown that compound 10 can only be co-assembled with a specific metal ion to achieve chiral amplification, and a circular dichroism signal can be detected.
Example 2
The preparation method of the water-soluble three-fork chiral molecule containing the azobenzene pyridine comprises the following steps:
compound 11 (2.81 g,3.16 mmol) (configuration S), compound 2 (1.69 g,3.16 mmol), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (1.81 g,9.44 mmol), 4-dimethylaminopyridine (47 mg,0.38 mmol) were placed in a 50ml flask at room temperature, and 20ml of acetonitrile solution was added to dissolve the whole. After the reaction was completed, the solvent was removed by rotary evaporation, and the mixture was separated by silica gel column chromatography (ethyl acetate/methanol, v1/v2=50/1) to obtain 4.00g of a yellow oily liquid compound 12.
Compound 12 (1.23 g,0.98 mmol) was placed in a 50ml flask containing 12ml of dichloromethane at room temperature and trifluoroacetic acid (3 ml,39.40 mmol) was slowly added dropwise to the reaction mixture. After stirring and reacting for 18h under air, triethylamine was slowly added dropwise to the reaction solution until no smoke was generated and white precipitate was generated, the product was extracted with dichloromethane, washed 3 times with saturated brine, and dried over anhydrous sodium sulfate. The solvent was removed by rotary evaporation to give 1.11g of Compound 13 as a yellow liquid.
Compound 13 (1.90 g,1.6 mmol) and Compound 5 (1.46 g,6.4 mmol) were dissolved in 70ml of N, N-dimethylformamide, 2-chloro-4, 6-dimethoxy-1, 3, 5-triazine (0.85 g,4.8 mmol) was added, after sonication (25 ℃ C., 100W) until the solution became clear, N-methylmorpholine (0.98 g,9.6 mmol) was added at 0 ℃ C., after stirring for 5min, the temperature was gradually raised to 90 ℃ C., stirring and refluxing under argon atmosphere for 24h, the solvent was removed by rotary evaporation, and silica gel column chromatography (dichloromethane/methanol, v1/v2=40/1) was separated to give 1.30g of a reddish brown solid compound 14 in 81% yield.
The specific synthetic route is as follows:
FIG. 7 is a photograph of compound 14 prepared in example 2 of the present invention 1 An H-NMR chart of the sample, 1 H NMR(400MHz,DMSO-d 6 )δ10.51(s,2H),8.94–8.82(m,4H),8.68(d,J＝7.8Hz,1H),8.27–8.19(m,4H),8.13–8.04(m,4H),7.97–7.90(m,4H),7.88–7.73(m,8H),7.57(t,J＝1.6Hz,1H),7.31–7.20(m,6H),7.18–7.16(m,1H),7.11(s,2H),4.73(ddd,J＝9.7,7.7,5.6Hz,1H),4.48(dddd,J＝24.5,9.0,5.9,2.6Hz,2H),4.36(dddd,J＝15.1,9.2,5.9,3.2Hz,2H),4.10(td,J＝4.5,2.6Hz,4H),4.05(dd,J＝5.7,4.2Hz,2H),3.74(t,J＝4.8Hz,4H),3.69–3.66(m,2H),3.65–3.43(m,32H),3.41(ddd,J＝7.6,5.8,3.9Hz,6H),3.21(s,9H)。
FIG. 8 is a schematic view of the ultraviolet absorption spectrum of the compound 14 prepared in example 2 of the present invention, wherein the maximum wavelength of the main ultraviolet absorption is 300nm. 24mg of compound 14 was dissolved in 3mL of water to give a brown-yellow clear aqueous solution at a concentration of 5mM, indicating that the chiral trigeminal molecule synthesized according to the present invention has good water solubility. FIG. 9 is a graphical representation of a tan clear aqueous solution of compound 14 prepared in example 2 of the present invention, and a circular dichroism spectrum test was performed on the aqueous solution of compound 14 (5 mM) under the high concentration condition, and the spectral result shows that the compound solution exhibits a significantly positive circular dichroism signal at an absorption wavelength of 300nm, which is just opposite to that of compound 10 (FIG. 4), indicating that compound 14 is a chiral molecule in S configuration. FIG. 10 is a schematic representation of the configurational circular dichroism spectrum signal of compound 14 prepared in example 2 of the present invention.
Use of the water-soluble, azo-benzene pyridine-containing, trigeminal chiral molecule in the preparation of chiral self-assemblies, the use comprising the steps of:
firstly, preparing a compound 14 into an aqueous solution with the concentration of 0.03mmol/L, and performing circular dichroism detection on the low-concentration aqueous solution, wherein the chirality of the obtained aqueous solution cannot be detected by the circular dichroism, and the signal detected by the circular dichroism is zero;
second, four parts of an aqueous solution (3 mL,0.03 mmol/L) of Compound 14 was prepared at room temperature, and metal chlorides (NaCl, cuCl) were added thereto, respectively 2 、CoCl 2 Or NiCl 2 ) The water solution is 9 mu L in dosage and 0.1mol/L in concentration, the mixed solution is uniformly shaken, kept stand and hatched for 7 days in a dark place, the compound 14 and the metal ions are co-assembled in the water solution through metal coordination, the co-assembled body is further subjected to super molecular assembly through non-covalent bond action to form a chiral self-assembled body, and the molar ratio of the compound 14 to the metal chloride is 1:10; the solution was subjected to circular dichroism detection, and the chirality of the obtained solution was effectively amplified, and a strong signal was detected by circular dichroism.
Compound 14The nanostructure of the chiral self-assembly is shown in fig. 11, and fig. 11 is a nanotopography of the chiral self-assembly formed after the compound 14 prepared in example 2 of the present invention and the metal thereof are co-assembled. The S-configuration of the trifurcated chiral molecules can be assembled into coil-like morphology in water, which indicates that the interaction and supramolecular assembly of the metal ions and the compound 14 do occur in the water solution, and a new supramolecular assembly is formed. The shape of the chiral self-assembled body formed after the chiral self-assembled body is assembled with metal can be changed, and the shape is different due to the different metal ions. Compound 14 and Co in aqueous solution 2+ Metal ion coordination co-assembly to form flaky film morphology like pine needle, and Na + Forming a seedling-like fibrous morphology, and Cu 2+ Forming the shape of the dendritic and regular arrangement of the petal-shaped particles and Ni 2+ Irregular aggregates are formed. This means that the supermolecule amplification effect produced by the coordinated co-assembly of compound 14 and the metal ion will vary from morphology to morphology.
FIG. 12 is a circular dichroism spectrum of chiral self-assembled hatching fluid formed after co-assembling compound 14 and metal thereof prepared in example 2 of the present invention, wherein an aqueous solution assembly of compound 14 has no circular dichroism spectrum signal, compound 14 and metal Ni 2+ Chiral self-assembly solution formed by ion mixing has no circular dichromatic signal, which indicates that the metal Ni 2+ The introduction of ions is detrimental to the chiral amplification of the co-assembly, but with Na + 、Cu 2+ And Co 2+ After the chiral self-assembly body is formed by ion coordination co-assembly, a strong signal with a circular dichroism expressed as negative chirality can be obtained through supermolecule chiral amplification, and the circular dichroism signal of the chiral co-assembly body has different intensities due to different morphologies of the co-assembly body, which means that the compound 14 can only realize chiral amplification by co-assembly with special metal ions, and the circular dichroism signal can be detected.
Comparative example 1
Only a few of the three-fork chiral molecules can be dissolved in water, and the three-fork chiral molecules with the chemical structural formula shown in the formula II are one of the three-fork chiral molecules.
FIG. 13 is a schematic view of the ultraviolet absorption spectrum of compound II of comparative example 1 of the present invention, wherein the wavelengths of the two main ultraviolet absorption are 264nm and 327nm, respectively. Similarly, four parts of an aqueous solution (3 mL,0.03 mmol/L) of Compound II was prepared at room temperature, and metal chlorides (NaCl, cuCl) were added thereto, respectively 2 、CoCl 2 Or NiCl 2 ) The water solution is 9 mu L, the concentration is 0.1mol/L, the mixed solution is uniformly shaken, and then the mixed solution is kept stand and hatched for 7 days in dark, and the mol ratio of the compound II to the metal chloride is 1:10; and (3) performing circular dichroism chromatography detection on the solution. FIG. 14 is a circular dichroism spectrum of a chiral self-assembled hatching fluid formed after co-assembling Compound II and its metal according to comparative example 1 of the present invention, an aqueous solution of Compound II has no circular dichroism spectrum signal, and Compound II and Metal Ni 2+ 、Na + 、Cu 2+ And Co 2+ The chiral self-assembly solution formed by ion mixing has no circular dichroism signal. The triple wishbone chiral molecules in the various embodiments of the present invention, which are associated with metallic Na + 、Cu 2+ And Co 2+ The chiral self-assembly body solution formed by ion coordination shows strong circular dichroism signals, so that the chiral self-assembly body solution has wider application in the fields of polarizing materials and the like.
The foregoing description is only illustrative of the preferred embodiment of the present invention, and is not to be construed as limiting the invention, but is to be construed as limiting the invention to any and all simple modifications, equivalent variations and adaptations of the embodiments described above, which are within the scope of the invention, may be made by those skilled in the art without departing from the scope of the invention.
Claims (7)
1. A water-soluble trigeminal chiral molecule containing azobenzene pyridine is characterized by having a general formula as follows:
wherein, represents R configuration or S configuration.
2. A method of preparing the water-soluble, azo-benzene pyridine-containing, trigeminal chiral molecule of claim 1, comprising the steps of:
wherein, represents R configuration or S configuration;
firstly, dissolving a chiral compound 1 and a chiral compound 2 in acetonitrile solution at room temperature, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 4-dimethylaminopyridine, stirring for 12-24 hours under the condition of room temperature and argon atmosphere, removing a solvent by rotary evaporation, and separating by silica gel column chromatography to obtain a compound 3;
the molar ratio of the compound 1 to the compound 2 is 1 (0.8-1.2), the molar ratio of the compound 1 to the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is 1 (1.2-3.5), and the molar ratio of the compound 1 to the 4-dimethylaminopyridine is 1 (0.1-0.2);
step two, adding the compound 3 into dichloromethane at room temperature, slowly dripping excessive trifluoroacetic acid, stirring for 12-24 hours in an air atmosphere, slowly dripping triethylamine into the reaction liquid until no smoke is generated and white precipitation is generated, extracting a product with dichloromethane, washing with saturated saline water, drying with anhydrous sodium sulfate, and removing a solvent by rotary evaporation to obtain a compound 4;
thirdly, dissolving the compound 4 and the compound 5 in N, N-dimethylformamide, adding 2-chloro-4, 6-dimethoxy-1, 3, 5-triazine, carrying out ultrasonic treatment until the solution becomes clear, adding N-methylmorpholine at 0 ℃, stirring for 3-8 min, gradually heating to 85-95 ℃, stirring for 12-24 h under argon atmosphere, removing the solvent by rotary evaporation, and separating by silica gel column chromatography to obtain the water-soluble trigeminal chiral molecule containing azobenzene pyridine;
the mol ratio of the compound 4 to the compound 5 is 1 (3-6); the mol ratio of the compound 4 to the 2-chloro-4, 6-dimethoxy-1, 3, 5-triazine is 1 (2-4); the mol ratio of the compound 4 to the N-methylmorpholine is 1 (5-7);
the chiral compound 1 has a configuration of R configuration or S configuration.
3. Use of the water-soluble azo-benzene pyridine-containing trigeminal chiral molecule of claim 1 in the preparation of chiral self-assemblies.
4. The application according to claim 3, characterized in that it comprises the following steps:
firstly, preparing water-soluble three-fork chiral molecules containing azobenzene pyridine into an aqueous solution, and performing circular dichroism detection on the aqueous solution, wherein the chirality of the obtained aqueous solution cannot be detected by the circular dichroism, and the signal detected by the circular dichroism is zero;
a second step of adding an aqueous solution of metal chloride selected from NaCl and CuCl into the aqueous solution of the first step and uniformly mixing 2 Or CoCl 2 The method comprises the steps of carrying out a first treatment on the surface of the Standing in dark for 5-10 days to form a chiral self-assembly body, wherein the molar ratio of the water-soluble trigeminal chiral molecule containing azobenzene pyridine to the metal chloride is 1 (8-15); the solution was subjected to circular dichroism detection, and the chirality of the obtained solution was effectively amplified, and a strong signal was detected by circular dichroism.
5. The use according to claim 4, wherein the concentration of the water-soluble aqueous solution of the azophenylpyridine-containing triple chiral molecule is 0.02 to 0.04mmol/L.
6. The use according to claim 4, wherein the concentration of the metal chloride solution is 0.05 to 0.15mol/L.
7. The use according to claim 4, wherein the molar ratio of the water-soluble, azo-benzene pyridine containing, trigeminal chiral molecule to the metal chloride is 1:10.
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| CN110407694A (en) * | 2019-07-31 | 2019-11-05 | 浙江大学 | A kind of water solubility column aromatic hydrocarbons Chiral amplification agent and its preparation method and application |
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