CN107141217B - A kind of chiral organic dye molecule and the preparation method and application thereof with blue-fluorescence - Google Patents
A kind of chiral organic dye molecule and the preparation method and application thereof with blue-fluorescence Download PDFInfo
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- CN107141217B CN107141217B CN201710282834.XA CN201710282834A CN107141217B CN 107141217 B CN107141217 B CN 107141217B CN 201710282834 A CN201710282834 A CN 201710282834A CN 107141217 B CN107141217 B CN 107141217B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 15
- -1 4- aminomethyl phenyl Chemical group 0.000 claims abstract description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 239000011737 fluorine Substances 0.000 claims abstract description 4
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 161
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 24
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 238000005698 Diels-Alder reaction Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 230000014759 maintenance of location Effects 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical group C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 8
- 230000003287 optical effect Effects 0.000 abstract description 6
- 230000005284 excitation Effects 0.000 abstract description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 abstract description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract description 2
- ORFSSYGWXNGVFB-UHFFFAOYSA-N sodium 4-amino-6-[[4-[4-[(8-amino-1-hydroxy-5,7-disulfonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound COC1=C(C=CC(=C1)C2=CC(=C(C=C2)N=NC3=C(C4=C(C=C3)C(=CC(=C4N)S(=O)(=O)O)S(=O)(=O)O)O)OC)N=NC5=C(C6=C(C=C5)C(=CC(=C6N)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] ORFSSYGWXNGVFB-UHFFFAOYSA-N 0.000 abstract description 2
- 150000003413 spiro compounds Chemical class 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 22
- 238000001228 spectrum Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000012795 verification Methods 0.000 description 8
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical group BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 6
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000000695 excitation spectrum Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000005311 nuclear magnetism Effects 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 230000021615 conjugation Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- CEBAHYWORUOILU-UHFFFAOYSA-N (4-cyanophenyl)boronic acid Chemical compound OB(O)C1=CC=C(C#N)C=C1 CEBAHYWORUOILU-UHFFFAOYSA-N 0.000 description 1
- VOAAEKKFGLPLLU-UHFFFAOYSA-N (4-methoxyphenyl)boronic acid Chemical compound COC1=CC=C(B(O)O)C=C1 VOAAEKKFGLPLLU-UHFFFAOYSA-N 0.000 description 1
- BIWQNIMLAISTBV-UHFFFAOYSA-N (4-methylphenyl)boronic acid Chemical compound CC1=CC=C(B(O)O)C=C1 BIWQNIMLAISTBV-UHFFFAOYSA-N 0.000 description 1
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical compound C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000003205 fragrance Substances 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
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002098 polyfluorene Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/57—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and carboxyl groups, other than cyano groups, bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- 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
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of chiral organic dye molecule and the preparation method and application thereof with blue-fluorescence.There are the optical activity enantiomeric excess of the structural formula left hand (M) as shown in formula (M) -1 and formula (P) -1 and the right hand (P) two kinds of spiral forms for the chirality organic dye molecule, in formula (M) -1 or formula (P) -1, Ar is selected from phenyl or substituted phenyl；The substituted phenyl is selected from least one of 4- aminomethyl phenyl, 4- methoxyphenyl, the fluorine-based phenyl of 4- and 4- cyano-phenyl.Chirality organic dye molecule of the invention is electrophilic aromatic diesters to be connected formation with distorted-structure through 6 member rings with dinaphthalene derivatives by methylene, while having the Spiro compounds being centainly conjugated again；After introducing additional aromatic substituent, fluorescent emission can be promoted, and structure more distorts, thus there is shorter excitation wavelength and launch wavelength, by taking Ar is phenyl as an example, the excitation wavelength in tetrahydrofuran is 344nm, launch wavelength is 439nm, shows almost pure blue in the solution.
Description
Technical field
The invention belongs to fluorescent material field more particularly to a kind of chiral organic dye molecule with blue-fluorescence and its
Preparation method and application.
Background technique
Blue organic luminous material has very high application in field of photovoltaic materials such as organic electroluminescence devices (OELD)
Value, and the chiral organic dyestuff of blue has important application value in circular polarization OLED (CP-OLED), 3D display field.By
It is one of red green blue tricolor in blue, if to obtain white light parts, blue light is necessary, however compared to red and green
Luminescent material, blue light material type is few, low efficiency, so finding efficient blue organic photoelectrical material is always numerous scientists
The hot spot of research.
At present in the field, representative blue-fluorescence molecule mainly has anthracene class and carbazole analog derivative (C.-
L.Wu, C.-H.Chang,Y.-T.Chang,C.-T.Chen,C.-T.Chen and C.-J.Su,High efficiency
non-dopant blue organic light-emitting diodes based on anthracene-based
fluorophores with molecular design of charge transport and red-shifted
emission proof,J.Mater.Chem.C,2014,2, 7188-7200；J.-Y.Hu,Y.-J.Pu,F.Satoh,
S.Kawata,H.Katagiri,H.Sasabe,and J.Kido, Bisanthracene-based donor–acceptor-
type light-emitting dopants:highly efficient deep-blue emission in organic
light-emitting devices,Adv.Funct.Mater.,2014,24,2064–2071)；Imidazole derivative (H.-
H.Chou,Y.-H.Chen,H.-P.Hsu,W.-H.Chang,Y.-H.Chen,and C.-H.Cheng, Synthesis of
diimidazolylstilbenes as n-type blue fluorophores:alternative dopant
materials for highly efficient electroluminescent devices,Adv.Mater.,2012,24,
5867–5871)；Delayed fluorescence class (M.Kim, S.K.Jeon, S.-H.Hwang, and J.Y.Lee, Stable blue
thermally activated delayed fluorescent organic light-emitting diodes with
three times longer lifetime than phosphorescent organic light-emitting
Diodes, Adv.Mater.2015,27,2515-2520) etc..
Conjugation (such as carbazoles, polyfluorene class etc.) and distortion electronics transfer have in the design synthesis of blue fluorescent material
Important role, be to design the important research of chiral blue fluorescent material in conjunction with twist structured electronics transfer and conjugation
Hot spot.
Summary of the invention
Chiral organic dye molecule that the object of the present invention is to provide a kind of with blue-fluorescence and preparation method thereof with answer
With.
It is provided by the invention chirality fluorescence distort conjugated compound, structural formula as shown in formula (M) -1 or formula (P) -1,
In formula (M) -1 and formula (P) -1, Ar is selected from phenyl or substituted phenyl；The substituted phenyl is selected from 4- methylbenzene
At least one of base, 4- methoxyphenyl, the fluorine-based phenyl of 4- and 4- cyano-phenyl.
In above-mentioned compound, compound shown in the formula (M) -1 concretely following formula (M) -1A to formula (M) -1E institute
Show any one in compound:
Compound shown in the formula (P) -1 is concretely any in compound shown in following formula (P) -1A to formula (P) -1E
It is a kind of:
Invention further provides the preparation methods of above-mentioned chiral fluorescence distortion conjugated compound, include the following steps:
(1) (chemical name 2,2 '-diphenyl -7,7 '-dimethoxy -3,4,3 ', the 4 '-tetrahydros-of compound shown in formula 2
1,1 '-binaphthalene) and formula 3 shown in compound (chemical name be butine dicarboxylic acid methyl ester) reacted through Diels-Alder, obtain
Compound shown in formula 4；
(2) compound shown in formula 4 and compound shown in formula 5 (chemical name 2, chloro- 5, the 6- dicyanoquinone of 3- bis-, letter
It is written as DDQ) through oxidation reaction, obtain compound shown in formula 6；Chiral resolution is carried out to compound shown in formula 6, obtains formula (M) -6
Compound shown in shown compound and formula (P) -6；
(3) existing for the alchlor under the conditions of, compound shown in compound shown in formula (M) -6 or formula (P) -6 and formula 7
Shown compound (chemical name is N-bromosuccinimide, is abbreviated as NBS) is substituted reaction, obtains formula (M) -8 shownization
Close compound shown in object or formula (P) -8；
(4) under inert gas protection, chemical combination shown in compound and formula 9 shown in compound shown in formula (M) -8 or formula (P) -8
Object, through Suzuki coupling reaction, can be obtained shown in compound shown in formula (M) -1 or formula (P) -1 under the action of palladium catalyst
Compound；
In formula 9, the same formula of the definition of Ar (M) -1 or formula (P) -1.
Above-mentioned preparation method, in step (1), the molar ratio of compound shown in compound shown in formula 3 and formula 2 can for (5~
10): 1, preferably 10:1.
The temperature of the Diels-Alder reaction can be 130~160 DEG C, preferably 140~150 DEG C；Time can be 6~10
Hour, preferably 8~10 hours.
The Diels-Alder reaction carries out in organic solvent, and the organic solvent can be in dimethylbenzene, o-dichlorohenzene
It is any.
Above-mentioned preparation method, in step (2), the molar ratio of compound shown in compound shown in formula 4 and formula 5 can be 1:(5
~12), preferably 1:10.
The temperature of the oxidation reaction can be 130~160 DEG C, preferably 140~150 DEG C；Time can be 8~12 hours, excellent
It selects 10~12 hours.
The oxidation reaction carries out in organic solvent, and the organic solvent can be any in dimethylbenzene, o-dichlorohenzene
Kind.
Above-mentioned preparation method, in step (2), the method for the chiral resolution be using high performance liquid chromatography chiral column into
Row is split.
The high performance liquid chromatography chiral column can beIE column.
Mobile phase used can be the mixed liquor of the n-hexane that volume ratio is 40:60 and methylene chloride composition.
The retention time of the compound shown in the formula (M) -6 can be 5.0~5.6min；Compound shown in the formula (P) -6
Retention time can be 2.8~3.4min.
Above-mentioned preparation method, in step (3), compound shown in compound shown in the formula (M) -6 or the formula (P) -6
Can be 1:(2~2.5 with the molar ratio of compound shown in formula 7 and alchlor): (2~2.5), preferably 1:2.2:2.3.
The temperature of the substitution reaction can be 18~25 DEG C, preferably 20 DEG C；Time can be 2~4 hours, preferably 2.5~3
Hour.
The substitution reaction carries out in organic solvent, and the organic solvent can be methylene chloride.
Above-mentioned preparation method, in step (4), shown in compound shown in the palladium catalyst, formula (M) -8 or formula (P) -8
The molar ratio of compound shown in compound and formula 9 can be (0.02~0.1): 1:(2~3), preferably 0.043:1:3.
The palladium catalyst includes but is not limited to triphenyl phosphorus palladium, palladium acetate, any in bis-triphenylphosphipalladium palladium dichloride
Kind.
The temperature of the Suzuki coupling reaction can be 90~130 DEG C, preferably 95~100 DEG C；Time can be small for 16~24
When, preferably 20~24 hours.
The Suzuki coupling reaction carries out in a solvent, and it is (8~5): (4~3) that the solvent, which is selected from by volume ratio:
Toluene, ethyl alcohol and the K of (3~1)2CO3The mixed liquor of aqueous solution composition is (8~5): (4~3): (3~1) by volume ratio
Dimethylbenzene, ethyl alcohol and K2CO3The mixed liquor of aqueous solution composition；The K2CO3The molar concentration of aqueous solution is 2mol/L.It is described molten
Agent toluene, ethyl alcohol and K that concretely volume ratio is 5:3:22CO3The mixed liquor of aqueous solution composition；The K2CO3Aqueous solution
Molar concentration is 2mol/L.
Above-mentioned chiral fluorescence distortion conjugated compound (compound shown in formula (M) -1 or formula (P) -1) has in preparation chirality
Application in machine luminescent material, also within the scope of the present invention.
The present invention also provides the intermediate for preparing above-mentioned chiral fluorescence distortion conjugated compound, structural formula such as formulas (M)-
Shown in 6 or shown in formula (P) -6,
Invention further provides the preparation methods of above-mentioned intermediate, include the following steps:
(1) compound shown in compound shown in formula 2 and formula 3 is reacted through Diels-Alder, obtains compound shown in formula 4；
(2) compound shown in formula 4 obtains compound shown in formula 6 with compound shown in formula 5 through oxidation reaction；To 6 institute of formula
Show that compound carries out chiral resolution, obtains compound shown in compound shown in formula (M) -6 and formula (P) -6；
Above-mentioned preparation method, in step (1), the molar ratio of compound shown in compound shown in formula 3 and formula 2 can for (5~
10): 1, preferably 10:1.
The temperature of the Diels-Alder reaction can be 130~160 DEG C, preferably 140~150 DEG C；Time can be 6~10
Hour, preferably 8~10 hours.
The Diels-Alder reaction carries out in organic solvent, and the organic solvent can be in dimethylbenzene, o-dichlorohenzene
It is any.
Above-mentioned preparation method, in step (2), the molar ratio of compound shown in compound shown in formula 4 and formula 5 can be 1:(5
~12), preferably 1:10.
The temperature of the oxidation reaction can be 130~160 DEG C, preferably 140~150 DEG C；Time can be 8~12 hours, excellent
It selects 10~12 hours.
The oxidation reaction carries out in organic solvent, and the organic solvent can be any in dimethylbenzene, o-dichlorohenzene.
Above-mentioned preparation method, in step (2), the method for the chiral resolution be using high performance liquid chromatography chiral column into
Row is split.
The high performance liquid chromatography chiral column can beIE column.
Mobile phase used can be the mixed liquor of the n-hexane that volume ratio is 40:60 and methylene chloride composition.
The retention time of the compound shown in the formula (M) -6 can be 5.0~5.6min；Compound shown in the formula (P) -6
Retention time can be 2.8~3.4min.
Chiral twist conjugated compound provided by the invention, since the compound is by methylene by electrophilic fragrance
Diester is connected with dinaphthalene derivatives through 6 member rings, and being formed has distorted-structure, while having the Spiro compounds being centainly conjugated again,
According to the difference of the hand of spiral, there are the optical activity enantiomeric excess of left hand (M) and the right hand (P) two kinds of spiral forms for compound.Draw
After entering additional aromatic substituent, fluorescent emission can be promoted, simultaneously because structure more distorts after introducing substituted aryl, because
And there is shorter excitation wavelength and launch wavelength, wherein (by taking Ar is phenyl as an example), the excitation wavelength in tetrahydrofuran is
344nm, launch wavelength 439nm.Almost pure blue is showed in the solution.It is provided by the invention to prepare above-mentioned distortion conjugation
The method of compound, raw material is cheap, and preparation process is simple, and synthetic yield is high, easy derivatization, commercial scale easy to accomplish,
Correct through instrument detection gained compound structure, stability is good, has a good application prospect in field of photovoltaic materials.
Detailed description of the invention
Fig. 1 is the synthetic route chart of chiral twist conjugated compound in embodiment 1.
Fig. 2 is the HPLC figure of racemoid shown in 1 Chinese style 6 of embodiment.
Fig. 3 is the HPLC figure that compound shown in the formula (M) -6 obtained later is split in embodiment 1.
Fig. 4 is the HPLC figure that compound shown in the formula (P) -6 obtained later is split in embodiment 1.
Fig. 5 is the nucleus magnetic hydrogen spectrum that embodiment 1 prepares gained chiral twist conjugated compound.
Fig. 6 is the nuclear-magnetism carbon spectrum that embodiment 1 prepares gained chiral twist conjugated compound.
Fig. 7 is the synthetic route chart of chiral twist conjugated compound in embodiment 2.
Fig. 8 is the nucleus magnetic hydrogen spectrum that embodiment 2 prepares gained chiral twist conjugated compound.
Fig. 9 is the nuclear-magnetism carbon spectrum that embodiment 2 prepares gained chiral twist conjugated compound.
Figure 10 is the synthetic route chart of chiral twist conjugated compound in embodiment 3.
Figure 11 is the nucleus magnetic hydrogen spectrum that embodiment 3 prepares gained chiral twist conjugated compound.
Figure 12 is the nuclear-magnetism carbon spectrum that embodiment 3 prepares gained chiral twist conjugated compound.
Figure 13 is the synthetic route chart of chiral twist conjugated compound in embodiment 4.
Figure 14 is the nucleus magnetic hydrogen spectrum that embodiment 4 prepares gained chiral twist conjugated compound.
Figure 15 is the nuclear-magnetism carbon spectrum that embodiment 4 prepares gained chiral twist conjugated compound.
Figure 16 is the synthetic route chart of chiral twist conjugated compound in embodiment 5.
Figure 17 is the nucleus magnetic hydrogen spectrum that embodiment 5 prepares gained chiral twist conjugated compound.
Figure 18 is the nuclear-magnetism carbon spectrum that embodiment 5 prepares gained chiral twist conjugated compound.
Figure 19 is the excitation spectrum (Figure 19 A) and transmitting light for the chiral twist conjugated compound being prepared in embodiment 1
It composes (Figure 19 B).
Figure 20 is the excitation spectrum (Figure 20 A) and transmitting light for the chiral twist conjugated compound being prepared in embodiment 2
It composes (Figure 20 B).
Figure 21 is the excitation spectrum (Figure 21 A) and transmitting light for the chiral twist conjugated compound being prepared in embodiment 3
It composes (Figure 21 B).
Figure 22 is the excitation spectrum (Figure 22 A) and transmitting light for the chiral twist conjugated compound being prepared in embodiment 4
It composes (Figure 22 B).
Figure 23 is the excitation spectrum (Figure 23 A) and transmitting light for the chiral twist conjugated compound being prepared in embodiment 5
It composes (Figure 23 B).
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
The trade name of chiral chromatographic column as used in the following examplesIE is purchased from Daicel drug
Chiral technology (Shanghai) Co., Ltd., article No. 85324.
Compound shown in embodiment 1, preparation formula (M) -1A and formula (P) -1A
According to compound shown in (the M) -1A of synthetic route preparation formula shown in Fig. 1 and formula (P) -1A, the specific steps are as follows:
1) 50g 2,2 '-diphenyl -7,7 '-dimethoxy -3,4,3 ' is sequentially added in 1000ml round-bottomed flask, 4 ' -
Tetrahydro -1,1 '-binaphthalene (structural formula is as shown in Equation 2), 150g butine dicarboxylic acid methyl ester (structural formula is as shown in Equation 3) and 500ml
Dimethylbenzene is heated to reflux 10 hours, cooling, is spin-dried for reaction solution, through chromatography column separating purification, is obtained 4 institute of 61.9g addition product formula
Show compound, yield 95%；Structure verification data are as follows:1H NMR(500MHz,CDCl3): δ 7.10 (tt, J=7.1,
1.3Hz, 2H), 6.99 (td, J=7.2,1.5Hz, 2H), 7.09 (d, J=6.0Hz, 4H), 6.86 (s, 2H), 6.77 (s,
2H), 6.14 (d, J=7.6Hz, 2H), 3.89 (s, 6H), 2.97 (s, 6H), 2.69-2.61 (m, 2H), 2.75 (td, J=
15.4,3.9Hz, 2H), 2.65 (t, J=15.0,4.2Hz, 2H) 2.14 (dt, J=14.2,3.1Hz, 2H), 1.34 (td, J=
14.7,4.1Hz,2H).13C NMR(126MHz,CDCl3):δ169.6,154.4,141.2, 137.0,136.1,135.8,
134.5,132.3,131.2,130.8,130.1,129.2,128.1,126.9,126.5,117.3, 59.4,52.5,38.8,
34.3,29.5.HRMS(APCI):m/z calcd for C40H37O6[M+H]+613.2357 found 613.2364. experience
Card, structure are correct.
2) compound, 60g DDQ (structural formula such as 5 institute of formula shown in 8g addition product formula 4 are added in 500ml round-bottomed flask
Show) and 300ml dimethylbenzene, after 12 hours, then filtering, a small amount of methylene chloride washing is spin-dried for, obtains through chromatography column separating purification
7.2g aoxidizes compound shown in addition product formula 6, yield 90%；Structure verification data are as follows:1H NMR(500MHz,
CDCl3): δ 7.03 (tt, J=7.3,1.4Hz, 2H), 6.97 (td, J=7.6,1.6Hz, 2H), 6.85 (dt, J=7.7,
1.4Hz, 4H), 6.77 (d, J=8.2Hz, 2H), 6.56 (dt, J=7.8,1.6Hz, 2H), 6.12 (dt, J=7.8,1.5Hz,
2H), 3.88 (s, 6H), 3.57 (s, 6H), 2.64 (ddd, J=15.4,4.0,2.4Hz, 2H), 2.35 (td, J=15.0,
4.2Hz, 2H), 2.14 (ddd, J=14.1,4.1,2.4Hz, 2H), 1.35-1.27 (m, 2H)13C NMR(126MHz,
CDCl3):δ169.0,155.5,138.3,137.3,136.4,136.0,134.1,130.9, 130.7,129.9,128.5,
127.2,127.0,126.8,125.7,111.2,56.3,52.4,29.4,28.1.HRMS(APCI): m/z calcd for
C40H35O6[M+H]+611.2389, found 611.2328. are verified, and structure is correct.
It is split by chiral chromatographic column, obtains compound shown in a pair of of chiral enantiomer formula (M) -6 and formula (P) -6 shownization
Close object；20 milligrams of samples are dissolved in 1.5ml milliliters of methylene chloride, are split by splitting condition as shown in table 1 below.
Table 1, splitting condition
The HPLC analysis data of table 2, racemic compound 6
The HPLC of compound shown in table 3, formula (M) -6 analyzes data
The HPLC of compound shown in table 4, formula (P) -6 analyzes data
The HPLC of racemoid formula 6 schemes as shown in Fig. 2, HPLC analysis data are as shown in table 2.Formula (M)-after fractionation
The HPLC of compound shown in 6 schemes as shown in figure 3, HPLC analysis data are as shown in table 3；The HPLC of compound shown in formula (P) -6 schemes
As shown in figure 4, HPLC analysis data are as shown in table 4.As upper spectrogram and analysis data it is found that split after formula (M) -6 shown in
The structure of compound shown in compound and formula (P) -6 is correct.
3) it is added in 250ml round-bottomed flask shown in compound shown in 1.5g oxidation addition product formula (M) -6 and formula (P) -6
Compound, 0.96g NBS (structural formula is as shown in Equation 7) and 0.8g alchlor react at room temperature 3 hours in 100ml methylene chloride,
It is spin-dried for reaction solution, after chromatography column separating purification, obtains chemical combination shown in compound shown in 1.8g product formula (M) -8 or formula (P) -8
Object, yield 95%；Structure verification data are as follows: 1H NMR (400MHz, CDCl3): δ 7.11 (s, 2H), 7.11-7.04 (m,
4H), 6.86 (s, 2H), 6.76 (s, 2H), 6.14 (d, J=7.6Hz, 2H), 3.89 (s, 6H), 2.97 (s, 6H), 2.65 (dt,
J=15.1,3.3Hz, 2H), 2.36 (td, J=15.3,3.9Hz, 2H), 2.14 (dt, J=14.3,3.2Hz, 2H), 1.34
(td, J=14.8,4.1Hz, 2H) .13C NMR (101MHz, CDCl3): δ 168.6,153.4,140.2,138.0,136.1,
135.7,135.5,133.3,131.3,130.2,130.0, 128.9,128.0,126.9,126.5,117.3,59.4,52.5,
29.3,27.5.HRMS(APCI):m/z calcd for C40H33Br2O6[M+H]+769.0545,found 766.0593.
Verified, structure is correct.
4) compound shown in compound shown in 320mg formula (M) -8 or formula (P) -8 and 508mg phenyl boric acid (structural formula such as formula are taken
Shown in 9A) it is added in bis- mouthfuls of bottles of 100ml, 25ml toluene and 15ml ethyl alcohol and 10ml is added with syringe under protection of argon gas
2mol/L K2CO3Catalyst triphenylphosphine palladium 20mg is added in aqueous solution, ventilation after five minutes, flows back 12 hours, takes organic layer,
MgSO4It dries, filters, is spin-dried for, obtained shown in hydrogenation helicene formula (the M) -1A or formula (P) -1A of phenyl substitution through pillar layer separation
Compound 219mg, yield 69%.Structure verification data are as follows:1H NMR (400MHz,CDCl3) δ 7.70 (d, J=1.4Hz,
2H), 7.68 (t, J=1.2Hz, 2H), 7.49-7.43 (m, 4H), 7.40-7.34 (m, 2H), 7.00 (tt, J=7.3,
1.4Hz, 2H), 6.97-6.91 (m, 4H), 6.90-6.83 (m, 4H), 6.24 (d, J=7.6Hz, 2H), 3.92 (s, 6H),
2.71 (s, 6H), 2.70-2.66 (m, 2H), 2.48 (td, J=15.2,3.8Hz, 2H), 2.23 (ddd, J=14.3,4.0,
2.3Hz, 2H), 1.45 (dd, J=15.2,4.7Hz, 2H) .HRMS (APCI) MS:763.3028 ([M+H]+).Related spectrogram is shown in
Fig. 5 and Fig. 6.Verified, structure is correct.
Compound shown in embodiment 2, preparation formula (M) -1B and formula (P) -1B
The preparation method is the same as that of Example 1, and the phenyl boric acid in step 4) is only replaced with to the 4- methylphenylboronic acid (structure of 595mg
Formula is as shown in formula 9B), synthetic route is as shown in fig. 7, obtain compound 244mg shown in (M) -1B and formula (P) -1B, yield 74%.
Structure verification data are as follows:1H NMR(500MHz,CDCl3) δ 7.59 (d, J=7.7Hz, 4H), 7.27-7.24 (m, 4H),
6.99 (t, J=7.4Hz, 2H), 6.93 (s, 4H), 6.85 (d, J=6.3Hz, 4H), 6.23 (d, J=7.6Hz, 2H), 3.91
(s, 6H), 2.71 (s, 6H), 2.70-2.65 (m, 2H), 2.48 (dd, J=15.3,4.0Hz, 2H), 2.43 (s, 6H), 2.22
(dd, J=13.7,3.2Hz, 2H), 1.42 (td, J=14.8,4.0Hz, 2H) .HRMS (APCI) MS:791.3367 ([M+H]+)。
Related spectrogram is shown in Fig. 8 and Fig. 9.Verified, structure is correct.
Compound shown in embodiment 3, preparation formula (M) -1C and formula (P) -1C
The preparation method is the same as that of Example 1, and the phenyl boric acid in step 4) is only replaced with to the 4- methoxyphenylboronic acid (knot of 610mg
Structure formula is as shown in formula 9C), synthetic route is as shown in Figure 10, obtains compound 251mg shown in (M) -1C and formula (P) -1C, yield
75%.Structure verification data are as follows:1H NMR(500MHz,CDCl3)δ7.64(s,2H),7.62 (s,2H),7.02–6.98(m,
6H), 6.93 (d, J=4.9Hz, 4H), 6.89-6.81 (m, 4H), 6.23 (d, J=7.6 Hz, 2H), 3.91 (s, 6H), 3.88
(s, 6H), 2.71 (s, 6H), 2.68 (d, J=3.4Hz, 2H), 2.46 (td, J=15.4,4.0Hz, 2H), 2.22 (dt, J=
13.9,3.1Hz, 2H), 1.42 (td, J=14.7,4.0Hz, 2H) .HRMS (APCI) MS:823.3265 ([M+H]+).It is related
Spectrogram is shown in Figure 11 and Figure 12.Verified, structure is correct.
Compound shown in embodiment 4, preparation formula (M) -1D and formula (P) -1D
The preparation method is the same as that of Example 1, the fluorine-based phenyl boric acid (structure of the 4- that the phenyl boric acid in step 4) is only replaced with 580mg
Formula is as shown in formula 9D), synthetic route is as shown in figure 13, obtains compound 253mg shown in (M) -1D and formula (P) -1D, yield
76%.Structure verification data are as follows:1H NMR(500MHz,CDCl3) δ 7.66 (dd, J=8.5,5.5Hz, 4H), 7.15 (t, J
=8.6Hz, 4H), 7.01 (t, J=7.3Hz, 2H), 6.95-6.82 (m, 8H), 6.23 (d, J=7.7 Hz, 2H), 3.92 (s,
6H), 2.75-2.70 (m, 2H), 2.68 (s, 6H), 2.47 (td, J=15.4,4.0Hz, 2H), 2.23 (dt, J=13.7,
3.2Hz, 2H), 1.44 (td, J=14.7,4.1Hz, 2H) .HRMS (APCI) MS:799.2826 ([M+H]+).Related spectrogram is shown in
Figure 14 and Figure 15.Verified, structure is correct.
Compound shown in embodiment 5, preparation formula (M) -1E and formula (P) -1E
The preparation method is the same as that of Example 1, and the phenyl boric acid in step 4) is only replaced with to the 4- cyanophenylboronic acid (structure of 590mg
Formula is as shown in formula 9E), synthetic route is as shown in figure 16, obtains compound 264mg shown in (M) -1E and formula (P) -1E, yield
78%.Structure verification data are as follows:1H NMR(400MHz,CDCl3) δ 7.82 (d, J=8.4Hz, 4H), 7.76 (d, J=
8.4Hz, 4H), 7.06-6.98 (m, 2H), 6.94 (s, 2H), 6.88 (td, J=7.3,1.3Hz, 4H), 6.82 (d, J=
7.9Hz, 2H), 6.23 (d, J=7.5Hz, 2H), 3.92 (s, 6H), 2.73 (ddd, J=15.6,4.1,2.2 Hz, 2H), 2.62
(s, 6H), 2.46 (td, J=15.4,3.9Hz, 2H), 2.26 (ddd, J=14.4,4.0,2.2Hz, 2H), 1.45 (td, J=
14.7,4.0Hz,2H).M HRMS(APCI)MS:813.2933([M+H]+).Related spectrogram is shown in Figure 17 and Figure 18.It is verified,
Structure is correct.
Embodiment 6
The conjugated compound that embodiment 1-5 is prepared is made into solvent with tetrahydrofuran and carries out uv-visible absorption spectra
With the measurement of fluorescence spectrum, 5 data of table are obtained.Ultra-violet absorption spectrum and fluorescence emission spectrum are shown in Figure 19-Figure 23.
The optical property of table 5, embodiment 1-5 preparation gained conjugated compound
Embodiment 7
Determinand makees solvent with tetrahydrofuran and carries out optical activity measurement (concentration is 1 milligram/ML), obtains 6 data of table, number
According to display, such compound has very high optical activity.
The optical activity of table 6, embodiment 1-5 preparation gained conjugated compound
Claims (10)
1. compound shown in formula (M) -1 or formula (P) -1,
In formula (M) -1 and formula (P) -1, Ar is selected from phenyl or substituted phenyl；The substituted phenyl is selected from 4- aminomethyl phenyl, 4-
At least one of the fluorine-based phenyl of methoxyphenyl, 4- and 4- cyano-phenyl.
2. compound according to claim 1, it is characterised in that: compound shown in the formula (M) -1 is specially following formula
(M) any one of -1A to formula (M) -1E:
Compound shown in the formula (P) -1 is specially any one of following formula (P) -1A to formula (P) -1E:
3. the preparation method of compound of any of claims 1 or 2, includes the following steps:
(1) compound shown in compound shown in formula 2 and formula 3 is reacted through Diels-Alder, obtains compound shown in formula 4；
(2) compound shown in formula 4 obtains compound shown in formula 6 with compound shown in formula 5 through oxidation reaction；To chemical combination shown in formula 6
Object carries out chiral resolution, obtains compound shown in compound shown in formula (M) -6 and formula (P) -6；
(3) existing for the alchlor under the conditions of, compound shown in compound shown in formula (M) -6 or formula (P) -6 and 7 shownization of formula
It closes object and is substituted reaction, obtain compound shown in compound shown in formula (M) -8 or formula (P) -8；
(4) under inert gas protection, compound shown in compound and formula 9 shown in compound shown in formula (M) -8 or formula (P) -8 exists
Through Suzuki coupling reaction under the action of palladium catalyst, chemical combination shown in compound shown in formula (M) -1 or formula (P) -1 can be obtained
Object；
In formula 9, the same formula of the definition of Ar (M) -1 or formula (P) -1.
4. preparation method according to claim 3, it is characterised in that: in step (1), shown in compound shown in formula 3 and formula 2
The molar ratio of compound is (5~10): 1；The temperature of the Diels-Alder reaction is 130~160 DEG C, and the time is 6~10 small
When；Diels-Alder reaction carries out in organic solvent, and the organic solvent is dimethylbenzene, any in o-dichlorohenzene
Kind；And/or
In step (2), the molar ratio of compound shown in compound shown in formula 4 and formula 5 is 1:(5~12)；The oxidation reaction
Temperature is 130~160 DEG C, and the time is 8~12 hours；The oxidation reaction carries out in organic solvent, and the organic solvent is
Any one of dimethylbenzene, o-dichlorohenzene；And/or
The method of the chiral resolution is split using high performance liquid chromatography chiral column；
The high performance liquid chromatography chiral column isIE column；
Mobile phase used is the mixed liquor of the n-hexane that volume ratio is 40:60 and methylene chloride composition；
The retention time of the compound shown in the formula (M) -6 is 5.0~5.6min；The reservation of compound shown in the formula (P) -6
Time is 2.8~3.4min.
5. preparation method according to claim 3 or 4, it is characterised in that: in step (3), chemical combination shown in the formula (M) -6
The molar ratio of compound shown in compound shown in object or the formula (P) -6 and formula 7 and alchlor is 1:(2~2.5): (2~
2.5)；The temperature of the substitution reaction is 18~25 DEG C, and the time is 2~4 hours；The substitution reaction in organic solvent into
Row, the organic solvent are methylene chloride；And/or
In step (4), chemical combination shown in compound shown in compound shown in the palladium catalyst, formula (M) -8 or formula (P) -8 and formula 9
The molar ratio of object is (0.02~0.1): 1:(2~3)；The palladium catalyst is triphenyl phosphorus palladium, palladium acetate and bi triphenyl phosphine
Any one of palladium chloride；The temperature of the Suzuki coupling reaction is 90~130 DEG C, and the time is 16~24 hours；It is described
Suzuki coupling reaction carries out in a solvent, and it is (8~5): (4~3) that the solvent, which is selected from by volume ratio: the toluene of (3~1),
Ethyl alcohol and K2CO3The mixed liquor of aqueous solution composition is (8~5): (4~3) by volume ratio: the dimethylbenzene of (3~1), ethyl alcohol with
K2CO3The mixed liquor of aqueous solution composition；The K2CO3The molar concentration of aqueous solution is 2mol/L.
6. compound shown in compound shown in formula (M) -6 or formula (P) -6,
7. the preparation method of compound as claimed in claim 6, includes the following steps:
(1) compound shown in compound shown in formula 2 and formula 3 is reacted through Diels-Alder, obtains compound shown in formula 4；
(2) compound shown in formula 4 obtains compound shown in formula 6 with compound shown in formula 5 through oxidation reaction；To chemical combination shown in formula 6
Object carries out chiral resolution, obtains compound shown in compound shown in formula (M) -6 or formula (P) -6；
8. preparation method as claimed in claim 7, it is characterised in that: in step (1), chemical combination shown in compound shown in formula 3 and formula 2
The molar ratio of object is (5~10): 1；The temperature of the Diels-Alder reaction is 130~160 DEG C, and the time is 6~10 hours；
The Diels-Alder is carried out in organic solvent, and the organic solvent is any one of dimethylbenzene, o-dichlorohenzene.
9. preparation method described in claim 7 or 8, it is characterised in that: in step (2), shown in compound shown in formula 4 and formula 5
The molar ratio of compound is 1:(5~12)；The temperature of the oxidation reaction is 130~160 DEG C, and the time is 8~12 hours；It is described
Oxidation reaction carries out in organic solvent, and the organic solvent is any one of dimethylbenzene, o-dichlorohenzene；And/or
The method of the chiral resolution is split using high performance liquid chromatography chiral column；The high performance liquid chromatography chiral column
ForIE column；Mobile phase used is the mixed liquor of the n-hexane that volume ratio is 40:60 and methylene chloride composition；
The retention time of the compound shown in the formula (M) -6 is 5.0~5.6min；The retention time of the compound shown in the formula (P) -6
For 2.8~3.4min.
10. compound shown in compound shown in formula (M) -1 of any of claims 1 or 2 or formula (P) -1 is in the chiral organic hair of preparation
Application in luminescent material.
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| CN105622356A (en) * | 2016-02-17 | 2016-06-01 | 中国科学院化学研究所 | Helicene diphenol hydride, method for preparing same and application of helicene diphenol hydride |
| CN106008318A (en) * | 2016-05-19 | 2016-10-12 | 中国科学院化学研究所 | Chiral organic dye molecules having circularly polarized luminescence properties as well as preparation method and application of chiral organic dye molecules |
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| CN105622356A (en) * | 2016-02-17 | 2016-06-01 | 中国科学院化学研究所 | Helicene diphenol hydride, method for preparing same and application of helicene diphenol hydride |
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