CN110194734A - Chiral fluorescent chemicals and the preparation method and application thereof based on the luxuriant alkane skeleton of ring - Google Patents
Chiral fluorescent chemicals and the preparation method and application thereof based on the luxuriant alkane skeleton of ring Download PDFInfo
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- 150000001335 aliphatic alkanes Chemical group 0.000 title claims abstract description 26
- 239000000126 substance Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 15
- 125000001424 substituent group Chemical group 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 78
- 229940125904 compound 1 Drugs 0.000 claims description 25
- 238000005859 coupling reaction Methods 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- -1 aryl boric acid Chemical compound 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000004327 boric acid Substances 0.000 claims description 7
- 150000001502 aryl halides Chemical class 0.000 claims description 4
- 238000007039 two-step reaction Methods 0.000 claims description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 230000021615 conjugation Effects 0.000 claims 1
- 238000004020 luminiscence type Methods 0.000 abstract description 21
- 230000004913 activation Effects 0.000 abstract description 2
- 230000003111 delayed effect Effects 0.000 abstract description 2
- 230000005281 excited state Effects 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 230000006872 improvement Effects 0.000 description 11
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000002983 circular dichroism Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- QBELEDRHMPMKHP-UHFFFAOYSA-N 1-bromo-2-chlorobenzene Chemical group ClC1=CC=CC=C1Br QBELEDRHMPMKHP-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 3
- UGOMMVLRQDMAQQ-UHFFFAOYSA-N xphos Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 UGOMMVLRQDMAQQ-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZWKNLRXFUTWSOY-QPJJXVBHSA-N (e)-3-phenylprop-2-enenitrile Chemical compound N#C\C=C\C1=CC=CC=C1 ZWKNLRXFUTWSOY-QPJJXVBHSA-N 0.000 description 1
- IYXVSRXFGYDNEV-UHFFFAOYSA-N 3-phenylprop-2-ynenitrile Chemical group N#CC#CC1=CC=CC=C1 IYXVSRXFGYDNEV-UHFFFAOYSA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- 101100497645 Leishmania donovani RAC-B gene Proteins 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/58—[b]- or [c]-condensed
- C07D209/70—[b]- or [c]-condensed containing carbocyclic rings other than six-membered
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
Abstract
The present invention relates to a kind of chiral fluorescent chemicals and the preparation method and application thereof based on the luxuriant alkane skeleton of ring.The present invention utilizes the skeleton structure of the luxuriant alkane rigidity of ring, so that it can be kept well excited state is chirality, to obtain very high luminous efficiency and good circular polarised luminescence performance (high dissymmetry factor).We can be with emission wavelength regulation and circular polarised luminescence (CPL) intensity and luminous intensity by changing R1, R2 substituent group.By changing R3 substituent group, molecule is set to be in electron donor/receive the state of electron, to obtain hot activation delayed fluorescence material.
Description
Technical field
The present invention relates to organic material and its preparation fields, more particularly, to a kind of chiral fluorescence based on the luxuriant alkane skeleton of ring
Compound and the preparation method and application thereof.
Background technique
Circular polarised luminescence is exactly the left-handed or right-circularly polarized light that a chiral luminescence system can issue varying strength
The phenomenon that, it can be used to study Chiral properties of the chiral material under excitation state.Compared to chiral molecules for polarised light
It absorbs, for luminescent organic molecule can be utilized to generate there is the research of circularly polarized light to be comparatively still in the primary stage.But
It is that circular polarised luminescence (Circularly Polarized Luminescence, abbreviation CPL) shows in 3D optics in recent years, believes
Potential use in terms of breath storage and the even asymmetric photochemical syntheses of transmission, confidential information imprinting, photoelectric device causes extensively
General concern, other than above-mentioned application, polarized-light technique can also be used in aviation and satellite remote sensing field.Therefore development tool
There are the chiral optical functional materials of polarized luminescence performance to have great importance.
The material that the CPL of early stage is used is mostly metal complex, this substance circular polarised luminescence performance with higher.
But there is also luminous efficiency is low, while the disadvantages of using non-renewable resources such as noble metals.
Small organic molecule luminescent material due to structure is simple, be easy to derivatization, be many kinds of many advantages, such as, thus become
The research hotspot in the field.But it is still difficult to obtain at present and is provided simultaneously with higher dissymmetry factor and high quantum production rate
Material.
The luxuriant alkane of ring is a kind of small organic molecule skeleton with relatively strong rigidity, is conducive to the molecule under excitation state and keeps preferable
Space structure, to obtain higher dissymmetry factor.Chromophore is introduced on this skeleton simultaneously, can be obtained higher
Fluorescence quantum yield.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of chiral fluorescent chemicals based on the luxuriant alkane skeleton of ring, the substances
With good circular polarised luminescence performance (CPL, Circularly Polarized Luminescence), while by changing not
Change emission wavelength, CPL intensity and fluorescence quantum yield with position substituent group, tool can also be prepared based on this molecular skeleton
There is the small organic molecule of heat lag performance.
The invention solves another technical problem be to provide a kind of chiral fluorescent chemicals based on the luxuriant alkane skeleton of ring
Preparation method.
The invention solves another technical problem be to provide a kind of chiral fluorescent chemicals based on the luxuriant alkane skeleton of ring
Application.
In order to solve the above technical problems, present invention provide the technical scheme that
A kind of chiral fluorescent chemicals based on the luxuriant alkane skeleton of chiral ring, the general structure of the compound are as follows:
Wherein R1Selected from H or aryl；R2Selected from aryl or unsaturated conjugated group；R3Selected from electron-withdrawing substituent
Aryl.
As the further improvement of technology, R2Selected from some representative structures listed below:
R3Selected from such structure listed below:
As the further improvement of technology, the compound includes the enantiomer of two kinds of configurations of R/S；Wherein S configuration mapping
The structure of body is as shown in general formula S-I:
Wherein the structure of R configuration enantiomer is as shown in general formula R-I:
As the further improvement of technology, the building of the compound basic framework is to pass through two-step reaction system from raw material 1
It is standby to obtain, wherein the structural formula of the raw material 1 is as follows:
As the further improvement of technology, the raw material 1 and adjacent chloro-bromobenzene react to obtain intermediate 1, in catalyzing by metal palladium
The lower generation coupling reaction of agent effect obtains compound 1, and synthetic route is as follows:
As the further improvement of technology, the intermediate 2 and intermediate 3 are prepared using following synthetic route:
As
The further improvement of technology, the intermediate 2 occur coupling reaction with aryl boric acid, obtain the similar materialization of the compound 1
Object 2 is closed, structure is as follows:
As the further improvement of technology, the intermediate 2 is reacted with olefin(e) compound, obtains the class of the compound 1
Like compounds 3, structure is as follows:
As the further improvement of technology, the intermediate 2 and acetylene hydrocarbon compound coupling reaction obtain the compound 1
Analog compounds 4, structure is as follows:
As the further improvement of technology, with aryl boric acid coupling reaction occurs for the intermediate 3, obtains the compound
1 analog compounds 5, structure is as follows:
As the further improvement of technology, with aryl halide coupling reaction occurs for the compound 1, obtains the chemical combination
The analog compounds 6 of object 1, structure is as follows:
Compared with prior art, the beneficial effects of the present invention are:
The present invention utilizes the skeleton structure of the luxuriant alkane rigidity of ring, so that it can preferably be protected excited state is chirality
It holds, to obtain very high dissymmetry factor.We are by changing R1、R2Substituent group can regulate and control luminous section, CPL intensity and
Luminous intensity.By changing R3Substituent group obtains hot activation delayed fluorescence material.
Detailed description of the invention
Fig. 1 is the circular dichroism figure of compound prepared by example 1.
Fig. 2 is the circular dichroism figure of compound prepared by example 2.
Fig. 3 is the circular dichroism figure of compound prepared by example 3.
Fig. 4 is the circular dichroism figure of compound prepared by example 4.
Fig. 5 is the circular dichroism figure of compound prepared by example 5.
Fig. 6 is the circular dichroism figure of compound prepared by example 6.
Fig. 7 is the circular dichroism figure of compound prepared by example 7.
Fig. 8 is the circular dichroism figure of compound prepared by example 8.
Fig. 9 is the circular polarised luminescence spectrogram of compound prepared by example 1.
Figure 10 is the circular polarised luminescence spectrogram of compound prepared by example 2.
Figure 11 is the circular polarised luminescence spectrogram of compound prepared by example 3.
Figure 12 is the circular polarised luminescence spectrogram of compound prepared by example 4.
Figure 13 is the circular polarised luminescence spectrogram of compound prepared by example 5.
Figure 14 is the circular polarised luminescence spectrogram of compound prepared by example 6.
Figure 15 is the circular polarised luminescence spectrogram of compound prepared by example 7.
Figure 16 is the circular polarised luminescence spectrogram of compound prepared by example 8.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
A kind of chiral fluorescent chemicals based on the luxuriant alkane skeleton of ring, the general structure of the compound are as follows:
Wherein R1Selected from H or aryl.
R2Selected from aryl or unsaturated conjugated group, such as some representative structures listed below:
R3Selected from the aryl for drawing electron substituent group, such as such structure listed below:
According to some embodiments of the present invention, the compound includes two kinds of enantiomers of R/S；Wherein its S type enantiomer
Structure as shown in general formula S-I:
The structure of its R type enantiomer is as shown in general formula R-I:
Wherein R1Selected from H or aryl.
R2Selected from aryl or unsaturated conjugated group, such as some representative structures listed below:
R3Selected from the aryl for drawing electron substituent group, such as such structure listed below:
According to some embodiments of the present invention, the building of its basic framework of the compound is passed through by raw material 1
Two-step reaction preparation, wherein the structural formula of the raw material 1 is as follows
According to some embodiments of the present invention, the raw material 1 and adjacent chloro-bromobenzene react to obtain intermediate 1, in Metal Palladium
Oxidative coupling occurs under catalyst action and obtains compound 1, synthetic route is as follows:
According to some embodiments of the present invention, the intermediate 2 and intermediate 3 are synthesized using following synthetic route:
According to
Certain embodiments of the invention, the intermediate 2 occur coupling reaction with aryl boric acid, obtain the similar of the compound 1
Compounds 2, structure is as follows:
According to some embodiments of the present invention, with olefin(e) compound coupling reaction occurs for the intermediate 2, obtains described
The analog compounds 3 of compound 1, structure is as follows:
According to some embodiments of the present invention, coupling reaction occurs for intermediate 2 and alkynyl compounds, obtains the chemical combination
The analog compounds 4 of object 1, structure is as follows:
According to some embodiments of the present invention, the intermediate 3 and aromatic yl acid reaction obtain the compound 1 and spread out
Biologic artifact 5, structure is as follows:
According to some embodiments of the present invention, the compound 1 is reacted with aryl halide, obtains the compound 1
Derivative compound 6, structure is as follows:
According to some embodiments of the present invention, the structure of compound shown in formula S-I is as shown in following formula S-I1 to S-I8:
According to some embodiments of the present invention, the structure of compound shown in formula R-I is as shown in following formula R-I1 to R-I8:
Compound shown in formula R-I is in compound shown in R-I1 to R-I6, and there are hands to chromophore's carbazole for the luxuriant alkane skeleton of ring
Property inductive effect, and the chiral induction is complete, thus makes the carbazole with face chirality with optical activity and can generate
The characteristic of good circular polarised luminescence.
Compound shown in formula R-I is in compound shown in R-I7 to R-I8, and there are chiralitys to lure to chromophore's carbazole for the luxuriant alkane of ring
Effect is led, and the chiral induction is complete, thus makes the carbazole with face chirality that there is optical activity and can generate very well
Circular polarised luminescence characteristic.Make between chromophore's carbazole and substituent group there are electron acceptor/electron donor structure simultaneously
It has the luminous characteristic of heat lag.
According to some embodiments of the present invention, the building of its basic framework of the compound is passed through by raw material 1
What two-step reaction synthesized, wherein the structural formula of the raw material 1 is as follows
According to some embodiments of the present invention, the raw material 1 and adjacent chloro-bromobenzene react to obtain intermediate 1, in Metal Palladium
Coupling obtains compound 1 under the action of catalyst, and synthetic route is as follows:
According to some embodiments of the present invention, the intermediate 2 and intermediate 3 are prepared using following synthetic route:
According to some embodiments of the present invention, the intermediate 2 and aryl boric acid coupling reaction, obtain the compound
1 analog compounds 2, structure is as follows:
According to some embodiments of the present invention, with olefin(e) compound coupling reaction occurs for the intermediate 2, obtains described
The analog compounds 3 of compound 1, structure is as follows:
According to some embodiments of the present invention, coupling reaction occurs for intermediate 2 and alkynyl compounds, obtains the chemical combination
The analog compounds 4 of object 1, structure is as follows:
According to some embodiments of the present invention, with aryl boric acid coupling reaction occurs for the intermediate 3, obtains describedization
1 analog 5 of object is closed, structure is as follows:
According to some embodiments of the present invention, the compound 1 and aryl halide coupling reaction, obtain the chemical combination
The analog compounds 6 of object 1, structure is as follows:
As described above, the carbazoles molecule based on the luxuriant alkane of ring has good circular polarised luminescence characteristic, show in 3D optics,
Information storage with transmission, confidential information imprinting, photoelectric device even asymmetry photochemical syntheses in terms of there is potential use
On the way.
The invention will be further described for following real column.Agents useful for same is unless otherwise specified in present invention implementation
It is commercially available.
Embodiment 1
Preparation formula S-I1 and formula R-I1 compound represented
Reaction equation is as follows:
Specific preparation process are as follows:
1) in the round-bottomed flask of 1L, the luxuriant alkane A of 40.0g bromo ring is dissolved in 600mL DMSO, with nitrogen as protection
Then gas sequentially adds 18.0g NaN3, 20.0g Cu2O and 38.4g Proline is stirred 2 days under conditions of 100 DEG C.Silica gel
Post separation obtains faint yellow product RAC-B, is then split with chiral column, yield 64%.
2) in the Schlenk pipe of 250mL, 6.0g B is dissolved in the toluene of 150mL, under argon atmosphere, successively
4.5g neighbour's chloro-bromobenzene, 0.6g Pd is added2(dba)3, 1.0g XPhos and 3.0g NaOt-Bu, then under conditions of 100 DEG C
It is stirred overnight, obtained material carries out column chromatography for separation, obtains white solid, yield 99%.
3) in the Schlenk pipe of 100mL, 4.0g C is dissolved in 34Ml DMA, using argon gas as protection gas, then
Sequentially add 1.1g Pd2(dba)3, 1.8g XPhos, 0.7g PivOH and 8.7gK2CO3, stirred under conditions of 100 DEG C
Night, obtained material carry out column chromatography for separation, obtain white solid, yield 63%
The gross production rate of final product R-I1 is 40%.The structure detection of the compound is as follows:
1H NMR (400MHz, Chloroform-d) δ 7.98 (d, J=7.9Hz, 1H), 7.80 (bras, 1H), 7.38
(d, J=8.0Hz, 1H), 7.32 (t, J=7.5Hz, 1H), 7.24-7.15 (m, 1H), 6.55 (d, J=7.5Hz, 1H), 6.48
(d, J=7.5Hz, 1H), 6.45-6.39 (m, 1H), 6.28 (dd, J=7.8,1.9 Hz, 1H), 5.85 (dd, J=7.7,
1.9Hz, 1H), 5.14 (dd, J=7.8,1.9Hz, 1H), 3.93 (dd, J=12.5,9.7Hz, 1H), 3.32-3.20 (m,
1H),3.10–2.82(m,6H).
13C NMR(126MHz,CDCl3)δ140.01,138.80,137.89,137.28,135.78,132.00,
131.47, 130.97,126.46,126.29,125.39,125.22,124.85,124.55,122.41,122.19,
119.66, 110.63,33.93,33.74,33.22,31.10.
Optical Rotation:Rp[α]22 D=6.8 (c=0.50, CHCl3)；
By testing result it is found that above compound structure is correct.
The gross production rate of gained final product S-I1 is 40%.The structure detection of the compound is as follows:
1H NMR (400MHz, Chloroform-d) δ 7.98 (d, J=7.9Hz, 1H), 7.80 (bras, 1H), 7.38
(d, J=8.0Hz, 1H), 7.32 (t, J=7.5Hz, 1H), 7.24-7.15 (m, 1H), 6.55 (d, J=7.5Hz, 1H), 6.48
(d, J=7.5Hz, 1H), 6.45-6.39 (m, 1H), 6.28 (dd, J=7.8,1.9 Hz, 1H), 5.85 (dd, J=7.7,
1.9Hz, 1H), 5.14 (dd, J=7.8,1.9Hz, 1H), 3.93 (dd, J=12.5,9.7Hz, 1H), 3.32-3.20 (m,
1H),3.10–2.82(m,6H).
13C NMR(126MHz,CDCl3)δ140.01,138.80,137.89,137.28,135.78,132.00,
131.47, 130.97,126.46,126.29,125.39,125.22,124.85,124.55,122.41,122.19,
119.66, 110.63,33.93,33.74,33.22,31.10.
Optical Rotation:Sp[α]22 D=-4.8 (c=0.50, CHCl3)；
By testing result it is found that above compound structure is correct.
Embodiment 2
Preparation formula S-I2 and formula R-I2 compound represented
Reaction equation is as follows:
Specific preparation process are as follows:
In the round-bottomed flask of 500mL, compound I1 is dissolved in 200mL acetonitrile, under conditions of -20 DEG C, is added
1.8g NBS continues to stir 4h with this condition, and resulting substance carries out column chromatography for separation, obtains white solid, yield 61%
In the Schlenk pipe of 10mL, compound C is dissolved in 2mL DMF and 0.26mL H2In O, sequentially add
31.8mg phenyl boric acid, 7.0mg Pd (PPh)4,82.8mg K2CO3, it is stirred overnight under the conditions of 100 DEG C, obtained material carries out column
Chromatography obtains white solid, yield 61%.
The gross production rate of final product R-I2 is 36%.The structure detection of the compound is as follows:
1H NMR (500MHz, Chloroform-d) δ 8.27 (d, J=1.7Hz, 1H), 7.91 (s, 1H), 7.78-7.72
(m, 2H), 7.66 (dd, J=8.3,1.7Hz, 1H), 7.55-7.48 (m, 3H), 7.40-7.35 (m, 1H), 6.65 (d, J=
7.5Hz, 1H), 6.59 (d, J=7.5Hz, 1H), 6.52 (dd, J=7.7,1.9 Hz, 1H), 6.38 (dd, J=7.8,2.0Hz,
1H), 5.99 (dd, J=7.8,2.0Hz, 1H), 5.36-5.26 (m, 1H), 4.07 (dd, J=12.8,9.7Hz, 1H), 3.43-
3.29(m,1H),3.19–2.93(m,6H).
13C NMR(126MHz,CDCl3)δ142.42,140.51,138.31,137.92,137.33,135.88,
133.23, 132.08,131.55,131.19,128.82,127.43,126.67,126.49,126.41,125.77,
125.54, 124.62,124.60,122.34,120.88,110.83,33.95,33.83,33.30,31.10.
Optical Rotation:Rp[α]22 D=107.2 (c=1.34, CHCl3)；
HRMS(ESI)calc for C28H22N[M-H]-372.1752.found 372.1756.
By testing result it is found that above compound structure is correct.
The gross production rate of final product S-I2 is 36%.The structure detection of the compound is as follows:
1H NMR (500MHz, Chloroform-d) δ 8.27 (d, J=1.7Hz, 1H), 7.91 (s, 1H), 7.78-7.72
(m, 2H), 7.66 (dd, J=8.3,1.7Hz, 1H), 7.55-7.48 (m, 3H), 7.40-7.35 (m, 1H), 6.65 (d, J=
7.5Hz, 1H), 6.59 (d, J=7.5Hz, 1H), 6.52 (dd, J=7.7,1.9 Hz, 1H), 6.38 (dd, J=7.8,2.0Hz,
1H), 5.99 (dd, J=7.8,2.0Hz, 1H), 5.36-5.26 (m, 1H), 4.07 (dd, J=12.8,9.7Hz, 1H), 3.43-
3.29(m,1H),3.19–2.93(m,6H).
13C NMR(126MHz,CDCl3)δ142.42,140.51,138.31,137.92,137.33,135.88,
133.23, 132.08,131.55,131.19,128.82,127.43,126.67,126.49,126.41,125.77,
125.54, 124.62,124.60,122.34,120.88,110.83,33.95,33.83,33.30,31.10.
Optical Rotation:Sp[α]22 D=-87.4 (c=0.57, CHCl3)；
HRMS(ESI)calc for C28H22N[M-H]-372.1752.found 372.1756.
By testing result it is found that above compound structure is correct.
Embodiment 3
Preparation formula S-I3 and formula R-I3 compound represented
Reaction equation is as follows:
Tool
Production procedure are as follows:
In the Schlenk pipe of 10mL, C is dissolved in 2mL DMF and 0.26mL H2In O, 38.2mg is sequentially added to cyanogen
Base phenyl boric acid, 7.0mg Pd (PPh)4,82.8mg K2CO3, obtained material carry out column chromatography for separation, obtain white solid, yield
57%.
The structure detection of the compound R-I3 is as follows:
1H NMR (500MHz, Chloroform-d) δ 8.26 (d, J=1.6Hz, 1H), 8.03 (s, 1H), 7.83 (d, J
=8.6Hz, 2H), 7.78 (d, J=8.2Hz, 2H), 7.65 (dd, J=8.4,1.6Hz, 1H), 7.56 (d, J=8.3Hz,
1H), 6.68 (d, J=7.4Hz, 1H), 6.61 (d, J=7.5Hz, 1H), 6.53 (dd, J=7.9,1.8Hz, 1H), 6.39
(dd, J=7.8,1.8Hz, 1H), 5.98 (dd, J=7.7,1.8Hz, 1H), 5.30 (d, J=1.3Hz, 1H), 4.05 (dd, J
=12.8,10.0Hz, 1H), 3.42-3.31 (m, 1H), 3.22-2.91 (m, 6H)
13C NMR(126MHz,CDCl3)δ146.88,140.63,139.01,137.79,137.42,135.89,
132.66, 132.21,131.65,131.58,130.94,127.78,126.99,126.34,125.93,125.29,
124.64, 124.37,122.55,121.10,119.35,111.25,109.80,33.93,33.84,33.30,31.07.
Optical Rotation:Rp[α]22 D=100.3 (c=0.73, CHCl3)；
HRMS(ESI)calc for C29H21N2[M-H]-397.1705.found 397.1694.
By testing result it is found that above compound structure is correct.
The structure detection of the compound R-I3 is as follows:
1H NMR (500MHz, Chloroform-d) δ 8.26 (d, J=1.6Hz, 1H), 8.03 (s, 1H), 7.83 (d, J
=8.6Hz, 2H), 7.78 (d, J=8.2Hz, 2H), 7.65 (dd, J=8.4,1.6Hz, 1H), 7.56 (d, J=8.3Hz,
1H), 6.68 (d, J=7.4Hz, 1H), 6.61 (d, J=7.5Hz, 1H), 6.53 (dd, J=7.9,1.8Hz, 1H), 6.39
(dd, J=7.8,1.8Hz, 1H), 5.98 (dd, J=7.7,1.8Hz, 1H), 5.30 (d, J=1.3Hz, 1H), 4.05 (dd, J
=12.8,10.0Hz, 1H), 3.42-3.31 (m, 1H), 3.22-2.91 (m, 6H)
13C NMR(126MHz,CDCl3)δ146.88,140.63,139.01,137.79,137.42,135.89,
132.66, 132.21,131.65,131.58,130.94,127.78,126.99,126.34,125.93,125.29,
124.64, 124.37,122.55,121.10,119.35,111.25,109.80,33.93,33.84,33.30,31.07.
Optical Rotation:Sp[α]22 D=-124.3 (c=0.79, CHCl3)；
HRMS(ESI)calc for C29H21N2[M-H]-397.1705.found 397.1694.
By testing result it is found that above compound structure is correct.
Embodiment 4
Preparation formula S-I4 and formula R-I4 compound represented
Reaction equation is as follows:
Tool
Production procedure are as follows:
In the Schlenk pipe of 10mL, 37.5mg compound C is dissolved in 0.5mL DMA, sequentially adds 12.7mg pairs
Cyano styrene, 0.6mg Pd (OAc)2,28.1uL Et3N and 15.2mg PPh3, it is stirred overnight under the conditions of 110 DEG C, gained
Substance carries out column chromatography for separation, obtains white solid, yield 63%.
Embodiment 5
Preparation formula S-I5 and formula R-I5 compound represented
Reaction equation is as follows:
Specifically
Preparation process are as follows:
In the Schlenk pipe of 10mL, 37.5mg compound C is dissolved in 0.25mL DMF, 15.3mg is sequentially added
To cyano phenylacetylene, 1.0mg Pd (PPh)3Cl2,0.4mg CuI,0.12mL Et3N and 7.9mg PPh3, under the conditions of 110 DEG C
It is stirred overnight, obtained material carries out column chromatography for separation, obtains white solid, yield 60%.
Embodiment 6
Preparation formula S-I6 and formula R-I6 compound represented
Reaction equation is as follows:
Specific preparation process are as follows:
In the Schlenk pipe of 10mL, 22.6mg compound D is dissolved in 1mL DMF and 0.3mL H2In O, successively plus
Enter 18.3mg phenyl boric acid, 1.0mg Pd (PPh)4,41.4mg K2CO3, it is stirred overnight under the conditions of 110 DEG C, obtained material carries out
Column chromatography for separation obtains white solid, yield 46%.
Embodiment 7
Preparation formula S-I7 and formula R-I7 compound represented
Reaction equation is as follows:
Specific preparation process are as follows:
In the Schlenk pipe of 10mL, 89.1mg compound 1 is dissolved in 0.5mL Isosorbide-5-Nitrae-dioxane, is sequentially added
97.2mg Trz-PhBr,11.3mg Pd(OAc)2, 30.0mg XPhos and 52.7mg NaOt-Bu stirs under the conditions of 80 DEG C
Overnight, obtained material carries out column chromatography for separation, obtains white solid, yield 49%.
Embodiment 8
Preparation formula S-I8 and formula R-I8 compound represented
Reaction equation is as follows:
Specific preparation process are as follows:
In the Schlenk pipe of 10mL, 148.5mg compound 1 is dissolved in 0.5mL DMSO, 72.7mg is added to fluorine
Benzene acetonitrile is stirred overnight under the conditions of 140 DEG C, and obtained material carries out column chromatography for separation, obtains white solid, yield 47%.Table
The optical property of lattice embodiment 1-3 prepare compound
The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, any ripe
Professional and technical personnel is known, without departing from the scope of the present invention, according to the technical essence of the invention, to above
Any simple modifications, equivalent substitutions and improvements etc., fall within the scope of protection of the technical scheme of the present invention made by embodiment
Within.
Claims (10)
1. a kind of chiral fluorescent chemicals based on the luxuriant alkane skeleton of ring, it is characterised in that: the general structure of the compound such as 1 institute of formula
Show:
Wherein R1Selected from H or aryl；R2Selected from aryl or conjugation group；R3Selected from the aryl for drawing electron substituent group.
2. the chiral fluorescent chemicals according to claim 1 based on the luxuriant alkane skeleton of ring, it is characterised in that: R2Selected from following
Structure:
R3Selected from having structure:
3. the chiral fluorescent chemicals according to claim 1 based on the luxuriant alkane skeleton of ring, it is characterised in that: the compound
Enantiomer comprising two kinds of configurations of R/S, the structure of planar chiral S configuration of compound is as shown in general formula S-1:
The structure of its R type enantiomer is as shown in general formula R -1:
4. the chiral fluorescent chemicals according to claim 1 based on the luxuriant alkane skeleton of ring, it is characterised in that: the compound base
The building of this skeleton is to be prepared from raw material 1 by two-step reaction, and the structural formula of the raw material 1 is as follows:
5. the chiral fluorescent chemicals according to claim 1 based on the luxuriant alkane skeleton of ring, it is characterised in that: use following conjunction
At route prepare compound 1:
6. the chiral fluorescent chemicals according to claim 5 based on the luxuriant alkane skeleton of ring, it is characterised in that: use following conjunction
Intermediate 2 and intermediate 3 are prepared at route:
7. the chiral fluorescent chemicals according to claim 6 based on the luxuriant alkane skeleton of ring, it is characterised in that: the intermediate
2 occur coupling reaction with aryl boric acid, obtain the analog compounds 2 of the compound 1；The intermediate 2 and olefinic compound
Coupling reaction occurs for object, obtains the analog compounds 3 of the compound 1；The intermediate 2 is coupled with acetylene hydrocarbon compound
Reaction, obtains the analog compounds 4 of the compound 1；Structure is as follows:
8. the chiral fluorescent chemicals according to claim 6 based on the luxuriant alkane skeleton of ring, it is characterised in that: the intermediate
3 occur coupling reaction with aryl boric acid, obtain the analog compounds 5 of the compound 1, structure is as follows:
9. the chiral fluorescent chemicals according to claim 6 based on the luxuriant alkane skeleton of ring, it is characterised in that: the compound
1 occurs coupling reaction with aryl halide, obtains the analog compounds 6 of the compound 1, structure is as follows:
10. application of the chiral fluorescent chemicals described in claim 1 based on the luxuriant alkane skeleton of ring as fluorescent material.
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