CN107141217A - A kind of chiral organic dye molecule with blue-fluorescence and preparation method and application - Google Patents
A kind of chiral organic dye molecule with blue-fluorescence and preparation method and application Download PDFInfo
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- CN107141217A CN107141217A CN201710282834.XA CN201710282834A CN107141217A CN 107141217 A CN107141217 A CN 107141217A CN 201710282834 A CN201710282834 A CN 201710282834A CN 107141217 A CN107141217 A CN 107141217A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000002795 fluorescence method Methods 0.000 title abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 15
- -1 aromatic diesters Chemical class 0.000 claims abstract description 5
- 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 168
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 20
- 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
- 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
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 229910000027 potassium carbonate 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
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 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
- 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
- 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
- 150000003413 spiro compounds Chemical class 0.000 abstract description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract 1
- 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
- 238000012360 testing method Methods 0.000 description 7
- 241001269238 Data Species 0.000 description 6
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical group BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-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
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy 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
- 238000005516 engineering process Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 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
- 230000015572 biosynthetic process Effects 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
- 238000001914 filtration Methods 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
- 230000003647 oxidation Effects 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 class 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
- 229940005561 1,4-benzoquinone Drugs 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
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000002474 experimental 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
- 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
- OSCBARYHPZZEIS-UHFFFAOYSA-N phenoxyboronic acid Chemical class OB(O)OC1=CC=CC=C1 OSCBARYHPZZEIS-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
- 241000894007 species Species 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 with blue-fluorescence and preparation method and application.There is the optical activity enantiomeric excess of left hand (M) and the right hand (P) two kind spiral form of the structural formula as shown in formula (M) 1 and formula (P) 1 in the chiral 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 phenyls, 4 methoxyphenyls, 4 fluorine-based phenyl and 4 cyano-phenyls.Chirality organic dye molecule of the invention is that electrophilic aromatic diesters are connected with dinaphthalene derivatives through 6 yuan of rings by methylene and formed with distorted-structure, while there is the Spiro compounds being necessarily conjugated again；Introduce after extra aromatic substituent, fluorescent emission can be promoted, and structure is more distorted, thus with shorter excitation wavelength and launch wavelength, so that Ar is phenyl as an example, the excitation wavelength in tetrahydrofuran is 344nm, launch wavelength is 439nm, and almost pure blueness is showed 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 technology
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 blueness has important application value in circular polarization OLED (CP-OLED), 3D display fields.By
It is one of red green blue tricolor in blueness, if to obtain white light parts, blue light is necessary, but compared to red and green
Luminescent material, blue light material species is few, and efficiency is low, so it is always numerous scientists to find efficient blue organic photoelectrical material
The focus 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 electro transfer have in the design synthesis of blue fluorescent material
Important effect, is the important research of the chiral blue fluorescent material of design with reference to twist structured electro transfer and conjugation
Focus.
The content of the invention
It is an object of the invention to provide a kind of chiral organic dye molecule with blue-fluorescence and preparation method thereof with answering
With.
Chiral fluorescence that the present invention is provided distortion conjugated compound, its 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- methylbenzenes
At least one of base, 4- methoxyphenyls, the fluorine-based phenyl of 4- and 4- cyano-phenyls.
In above-mentioned compound, compound shown in the formula (M) -1 concretely following formula (M) -1A to formula (M) -1E institutes
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 method that above-mentioned chiral fluorescence distorts conjugated compound, comprise the following steps：
(1) compound shown in formula 2 (chemical name is 2,2 '-diphenyl -7,7 '-dimethoxy -3,4,3 ', 4 '-tetrahydrochysene -
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) (chemical name is chloro- 5, the 6- dicyan 1,4-benzoquinone of 2,3- bis- to compound shown in formula 4, letter with compound shown in formula 5
It is written as DDQ) oxidized reaction, obtain compound shown in formula 6；Chiral resolution is carried out to compound shown in formula 6, formula (M) -6 is obtained
Compound shown in shown compound and formula (P) -6；
(3) under conditions of alchlor presence, 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
Compound shown in compound or formula (P) -8；
(4) under inert gas shielding, compound shown in compound shown in formula (M) -8 or formula (P) -8 and chemical combination shown in formula 9
Thing is in the presence of palladium catalyst through Suzuki coupling reactions, you can obtain shown in compound shown in formula (M) -1 or formula (P) -1
Compound；
In formula 9, the Ar same formula of definition (M) -1 or formula (P) -1.
In above-mentioned preparation method, step (1), the mol ratio of compound shown in formula 3 and compound shown in formula 2 can for (5~
10)：1, preferably 10：1.
The temperature of the Diels-Alder reactions can be 130~160 DEG C, preferably 140~150 DEG C；Time can be 6~10
Hour, preferably 8~10 hours.
The Diels-Alder reactions are carried out in organic solvent, and the organic solvent can be in dimethylbenzene, o-dichlorohenzene
It is any.
In above-mentioned preparation method, step (2), the mol ratio of compound shown in formula 4 and compound shown in 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
Select 10~12 hours.
The oxidation reaction is carried out in organic solvent, and the organic solvent can be any in dimethylbenzene, o-dichlorohenzene
Kind.
In above-mentioned preparation method, step (2), the method for the chiral resolution is entered using high performance liquid chromatography chiral column
Row is split.
The high performance liquid chromatography chiral column can beIE posts.
Mobile phase used can be that volume ratio is 40：The mixed liquor of 60 n-hexane and dichloromethane composition.
The retention time of 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.
In above-mentioned preparation method, step (3), compound shown in compound shown in the formula (M) -6 or the formula (P) -6
Can be 1 with compound shown in formula 7 and the mol ratio of alchlor：(2~2.5)：(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 is carried out in organic solvent, and the organic solvent can be dichloromethane.
In above-mentioned preparation method, step (4), shown in compound shown in the palladium catalyst, formula (M) -8 or formula (P) -8
The mol ratio of compound and compound shown in formula 9 can be (0.02~0.1)：1：(2~3), preferably 0.043：1： 3.
Any that the palladium catalyst includes but is not limited in triphenyl phosphorus palladium, palladium, bis-triphenylphosphipalladium palladium dichloride
Kind.
The temperature of the Suzuki coupling reactions 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 reactions are carried out in a solvent, and it is (8~5) that the solvent, which is selected from by volume ratio,：(4~3)：
Toluene, ethanol and the K of (3~1)2CO3The mixed liquor of aqueous solution composition is (8~5) by volume ratio：(4~3)：(3~1)
Dimethylbenzene, ethanol and K2CO3The mixed liquor of aqueous solution composition；The K2CO3The molar concentration of the aqueous solution is 2mol/L.It is described molten
Concretely volume ratio is 5 for agent：3：2 toluene, ethanol and K2CO3The mixed liquor of aqueous solution composition；The K2CO3The aqueous 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.
Present invention also offers the intermediate for preparing above-mentioned chiral fluorescence and distorting conjugated compound, its structural formula such as formula (M)-
Shown in 6 or shown in formula (P) -6,
Invention further provides the preparation method of above-mentioned intermediate, comprise 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 and the oxidized reaction of compound shown in formula 5, obtain compound shown in formula 6；To the institute of formula 6
Show that compound carries out chiral resolution, obtain compound shown in compound shown in formula (M) -6 and formula (P) -6；
In above-mentioned preparation method, step (1), the mol ratio of compound shown in formula 3 and compound shown in formula 2 can for (5~
10)：1, preferably 10：1.
The temperature of the Diels-Alder reactions can be 130~160 DEG C, preferably 140~150 DEG C；Time can be 6~10
Hour, preferably 8~10 hours.
The Diels-Alder reactions are carried out in organic solvent, and the organic solvent can be in dimethylbenzene, o-dichlorohenzene
It is any.
In above-mentioned preparation method, step (2), the mol ratio of compound shown in formula 4 and compound shown in 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
Select 10~12 hours.
The oxidation reaction is carried out in organic solvent, and the organic solvent can be any in dimethylbenzene, o-dichlorohenzene.
In above-mentioned preparation method, step (2), the method for the chiral resolution is entered using high performance liquid chromatography chiral column
Row is split.
The high performance liquid chromatography chiral column can beIE posts.
Mobile phase used can be that volume ratio is 40：The mixed liquor of 60 n-hexane and dichloromethane composition.
The retention time of 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.
The chiral twist conjugated compound that the present invention is provided, because the compound is by electrophilic fragrance by methylene
Diester is connected with dinaphthalene derivatives through 6 yuan of rings, and being formed has distorted-structure, while have the Spiro compounds being necessarily conjugated again,
According to the difference of the hand of spiral, there is the optical activity enantiomeric excess of left hand (M) and the right hand (P) two kinds of spiral forms in compound.Draw
Enter after extra aromatic substituent, fluorescent emission can be promoted, simultaneously because introducing after substituted aryl, structure is more distorted, because
And with shorter excitation wavelength and launch wavelength, wherein (so that Ar is phenyl as an example), the excitation wavelength in tetrahydrofuran is
344nm, launch wavelength is 439nm.Almost pure blueness is showed in the solution.What the present invention was provided prepares above-mentioned distortion conjugation
The method of compound, raw material is cheap, and preparation technology is simple, and synthetic yield is high, and easy derivatization easily realizes commercial scale,
Detect that gained compound structure is correct through instrument, stability is good, has good application prospect in field of photovoltaic materials.
Brief description of the drawings
Fig. 1 is the synthetic route chart of chiral twist conjugated compound in embodiment 1.
Fig. 2 schemes for the HPLC of racemoid shown in the Chinese style 6 of embodiment 1.
Fig. 3 is the HPLC figures of compound shown in obtained formula (M) -6 after splitting in embodiment 1.
Fig. 4 is the HPLC figures of compound shown in obtained formula (P) -6 after splitting 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 of the chiral twist conjugated compound prepared in embodiment 1
Compose (Figure 19 B).
Figure 20 is the excitation spectrum (Figure 20 A) and transmitting light of the chiral twist conjugated compound prepared in embodiment 2
Compose (Figure 20 B).
Figure 21 is the excitation spectrum (Figure 21 A) and transmitting light of the chiral twist conjugated compound prepared in embodiment 3
Compose (Figure 21 B).
Figure 22 is the excitation spectrum (Figure 22 A) and transmitting light of the chiral twist conjugated compound prepared in embodiment 4
Compose (Figure 22 B).
Figure 23 is the excitation spectrum (Figure 23 A) and transmitting light of the chiral twist conjugated compound prepared in embodiment 5
Compose (Figure 23 B).
Embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material, reagent used etc., unless otherwise specified, are commercially obtained in following embodiments.
The trade name of chiral chromatographic column used in following embodimentsIE, purchased from Daicel medicine
Chiral technology (Shanghai) Co., Ltd., article No. is 85324.
Embodiment 1, formula (M) -1A and compound shown in formula (P) -1A
According to compound shown in (the M) -1A of synthetic route formula shown in Fig. 1 and formula (P) -1A, comprise the following steps that：
1) 50g 2,2 '-diphenyl -7,7 is sequentially added in 1000ml round-bottomed flasks '-dimethoxy -3,4,3 ', 4 ' -
Tetrahydrochysene -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 chromatogram column separating purification, obtains the institute of 61.9g addition compound products formula 4
Show compound, yield is 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. experiences
Card, structure is correct.
2) compound, 60g DDQ (the structural formula such as institutes of formula 5 shown in 8g addition compound products formula 4 are added in 500ml round-bottomed flasks
Show) and 300ml dimethylbenzene, after 12 hours, then filtering, a small amount of dichloromethane washing is spin-dried for, is obtained through chromatogram column separating purification
Compound shown in 7.2g oxidation addition compound products formula 6, yield is 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. empirical tests, structure is correct.
Split by chiral chromatographic column, obtain compound shown in a pair of chiral enantiomer formulas (M) -6 and formula (P) -6 shownization
Compound；20 milligrams of samples are dissolved in 1.5ml milliliters of dichloromethane, split by splitting condition as shown in table 1 below.
Table 1, splitting condition
The HPLC analyze datas of table 2, racemic compound 6
The HPLC analyze datas of compound shown in table 3, formula (M) -6
The HPLC analyze datas of compound shown in table 4, formula (P) -6
The HPLC of racemoid formula 6 is schemed as shown in Fig. 2 HPLC analyze datas are as shown in table 2.Formula (M) after fractionation-
The HPLC of compound shown in 6 is schemed as shown in figure 3, HPLC analyze datas are as shown in table 3；The HPLC figures of compound shown in formula (P) -6
As shown in figure 4, HPLC analyze datas are as shown in table 4.From upper spectrogram and analyze data, shown in the formula (M) -6 after fractionation
The structure of compound is correct shown in compound and formula (P) -6.
3) added in 250ml round-bottomed flasks shown in compound shown in 1.5g oxidation addition compound product formulas (M) -6 and formula (P) -6
Compound, 0.96g NBS (structural formula is as shown in Equation 7) and 0.8g alchlors, are reacted at room temperature 3 hours in 100ml dichloromethane,
Reaction solution is spin-dried for, after chromatogram column separating purification, chemical combination shown in compound shown in 1.8g products formula (M) -8 or formula (P) -8 is obtained
Thing, yield 95%；Structure verification data are as follows：1H NMR(400MHz,CDCl3): δ7.11(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):δ168.6,153.4,140.2,138.0,136.1,
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.
Empirical tests, structure is correct.
4) compound shown in compound shown in 320mg formulas (M) -8 or formula (P) -8 and 508mg phenyl boric acids (structural formula such as formula are taken
Shown in 9A) add in bis- mouthfuls of bottles of 100ml, add 25ml toluene and 15ml ethanol and 10ml with syringe under argon gas protection
2mol/L K2CO3The aqueous solution, ventilation adds catalyst triphenylphosphine palladium 20mg after 5 minutes, flows back 12 hours, takes organic layer,
MgSO4Dry, filtering is spin-dried for, obtained through pillar layer separation shown in hydrogenation helicene formula (the M) -1A or formula (P) -1A of phenyl substitution
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.Empirical tests, structure is correct.
Embodiment 2, formula (M) -1B and compound shown in formula (P) -1B
Preparation method be the same as Example 1, only by step 4) in phenyl boric acid replace with 595mg 4- methylphenylboronic acid (structures
Formula is as shown in formula 9B), synthetic route is as shown in fig. 7, obtain compound 244mg, yield 74% shown in (M) -1B and formula (P) -1B.
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.Empirical tests, structure is correct.
Embodiment 3, formula (M) -1C and compound shown in formula (P) -1C
Preparation method be the same as Example 1, only by step 4) in phenyl boric acid replace with 610mg 4- methoxyphenylboronic acids (knot
Structure formula is as shown in formula 9C), synthetic route as shown in Figure 10, obtains compound 251mg, yield shown in (M) -1C and formula (P) -1C
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.Empirical tests, structure is correct.
Embodiment 4, formula (M) -1D and compound shown in formula (P) -1D
Preparation method be the same as Example 1, only by step 4) in phenyl boric acid replace with 580mg fluorine-based phenyl boric acid (structures of 4-
Formula is as shown in formula 9D), synthetic route as shown in figure 13, obtains compound 253mg, yield shown in (M) -1D and formula (P) -1D
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.Empirical tests, structure is correct.
Embodiment 5, formula (M) -1E and compound shown in formula (P) -1E
Preparation method be the same as Example 1, only by step 4) in phenyl boric acid replace with 590mg 4- cyanophenylboronic acid (structures
Formula is as shown in formula 9E), synthetic route as shown in figure 16, obtains compound 264mg, yield shown in (M) -1E and formula (P) -1E
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.Empirical tests,
Structure is correct.
Embodiment 6
The conjugated compound that embodiment 1-5 is prepared makees solvent with tetrahydrofuran and carries out uv-visible absorption spectra
With the measure of fluorescence spectrum, the data of table 5 are obtained.Ultra-violet absorption spectrum and fluorescence emission spectrum are shown in Figure 19-Figure 23.
Table 5, embodiment 1-5 prepare the optical property of gained conjugated compound
Embodiment 7
Determinand makees solvent using tetrahydrofuran and carries out optical activity measure (concentration is 1 milligram/ML), obtains the data of table 6, number
According to display, such compound has very high optical activity.
Table 6, embodiment 1-5 prepare the optical activity of 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 phenyls, 4-
At least one of the fluorine-based phenyl of methoxyphenyl, 4- and 4- cyano-phenyls.
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 the compound described in claim 1 or 2, comprises 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 and the oxidized reaction of compound shown in formula 5, obtain compound shown in formula 6；To chemical combination shown in formula 6
Thing carries out chiral resolution, obtains compound shown in compound shown in formula (M) -6 and formula (P) -6；
(3) under conditions of alchlor presence, compound shown in compound shown in formula (M) -6 or formula (P) -6 and shownization of formula 7
Compound is substituted reaction, obtains compound shown in compound shown in formula (M) -8 or formula (P) -8；
(4) under inert gas shielding, compound shown in compound shown in formula (M) -8 or formula (P) -8 exists with compound shown in formula 9
Through Suzuki coupling reactions in the presence of palladium catalyst, you can obtain chemical combination shown in compound shown in formula (M) -1 or formula (P) -1
Thing；
In formula 9, the Ar same formula of definition (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 mol ratio of compound is (5~10)：1；The temperature of the Diels-Alder reactions is 130~160 DEG C, and the time is 6~10 small
When；The Diels-Alder reactions are carried out in organic solvent, and the organic solvent is any in dimethylbenzene, o-dichlorohenzene
Kind；And/or,
In step (2), the mol ratio of compound shown in formula 4 and compound shown in 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 is carried out in organic solvent, and the organic solvent is
Any 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 posts；
Mobile phase used is that volume ratio is 40：The mixed liquor of 60 n-hexane and dichloromethane composition；
The retention time of 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. the preparation method according to claim 3 or 4, it is characterised in that：In step (3), chemical combination shown in the formula (M) -6
Compound shown in thing or the formula (P) -6 is 1 with compound shown in formula 7 and the mol ratio of alchlor：(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 is entered in organic solvent
OK, the organic solvent is dichloromethane；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 mol ratio of thing is (0.02~0.1)：1：(2~3)；The palladium catalyst is triphenyl phosphorus palladium, palladium and bi triphenyl phosphine
Any of palladium chloride；The temperature of the Suzuki coupling reactions is 90~130 DEG C, and the time is 16~24 hours；It is described
Suzuki coupling reactions are carried out in a solvent, and it is (8~5) that the solvent, which is selected from by volume ratio,：(4~3)：The toluene of (3~1),
Ethanol and K2CO3The mixed liquor of aqueous solution composition is (8~5) by volume ratio：(4~3)：The dimethylbenzene of (3~1), ethanol with
K2CO3The mixed liquor of aqueous solution composition；The K2CO3The molar concentration of the aqueous solution is 2mol/L.
6. compound shown in compound shown in formula (M) -6 or formula (P) -6,
7. the preparation method of the compound described in claim 6, comprises 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 and the oxidized reaction of compound shown in formula 5, obtain compound shown in formula 6；To chemical combination shown in formula 6
Thing carries out chiral resolution, obtains compound shown in compound shown in formula (M) -6 or formula (P) -6；
8. the preparation method described in claim 7, it is characterised in that：In step (1), compound shown in formula 3 and chemical combination shown in formula 2
The mol ratio of thing is (5~10)：1；The temperature of the Diels-Alder reactions 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 of dimethylbenzene, o-dichlorohenzene.
9. the 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 mol 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 is carried out in organic solvent, and the organic solvent is any 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 posts；Mobile phase used is that volume ratio is 40：The mixed liquor of 60 n-hexane and dichloromethane composition；
The retention time of compound shown in the formula (M) -6 is 5.0~5.6min；The retention time of compound shown in the formula (P) -6
For 2.8~3.4min.
10. compound shown in compound shown in the formula (M) -1 described in claim 1 or 2 or formula (P) -1 is preparing chiral organic hair
Application in luminescent material.
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