CN105461743B - Double symmetrical aryl derivatives of miscellaneous five-membered ring and preparation method thereof - Google Patents
Double symmetrical aryl derivatives of miscellaneous five-membered ring and preparation method thereof Download PDFInfo
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- CN105461743B CN105461743B CN201610006548.6A CN201610006548A CN105461743B CN 105461743 B CN105461743 B CN 105461743B CN 201610006548 A CN201610006548 A CN 201610006548A CN 105461743 B CN105461743 B CN 105461743B
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- -1 silane compound Chemical class 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 7
- VCPPTNDHEILJHD-UHFFFAOYSA-N lithium;prop-1-ene Chemical compound [Li+].[CH2-]C=C VCPPTNDHEILJHD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 6
- 229910003074 TiCl4 Inorganic materials 0.000 claims abstract description 5
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000011368 organic material Substances 0.000 claims description 3
- 239000005046 Chlorosilane Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 230000031709 bromination Effects 0.000 claims 1
- 238000005893 bromination reaction Methods 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 229910052710 silicon Inorganic materials 0.000 abstract description 7
- 239000010703 silicon Substances 0.000 abstract description 7
- 230000003287 optical effect Effects 0.000 abstract description 4
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 abstract description 3
- 229910001623 magnesium bromide Inorganic materials 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000006356 dehydrogenation reaction Methods 0.000 abstract 2
- 229910000077 silane Inorganic materials 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 230000021615 conjugation Effects 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- AFZZYIJIWUTJFO-UHFFFAOYSA-N 1,3-diethylbenzene Chemical compound CCC1=CC=CC(CC)=C1 AFZZYIJIWUTJFO-UHFFFAOYSA-N 0.000 description 1
- 0 CC*c1c(*(C(C2N(CC(C3)*3=C)*3c4c(*)cc(*)cc4*)c4ccccc4)NC2=C3c2ccccc2)c(O)cc(*)c1 Chemical compound CC*c1c(*(C(C2N(CC(C3)*3=C)*3c4c(*)cc(*)cc4*)c4ccccc4)NC2=C3c2ccccc2)c(O)cc(*)c1 0.000 description 1
- 235000004237 Crocus Nutrition 0.000 description 1
- 241000596148 Crocus Species 0.000 description 1
- LCLVWYNFALMZHY-UHFFFAOYSA-N [Si].C1=CC=CC=C1.O1C(=O)C=CC2=CC=CC=C12 Chemical class [Si].C1=CC=CC=C1.O1C(=O)C=CC2=CC=CC=C12 LCLVWYNFALMZHY-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 235000021384 green leafy vegetables Nutrition 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- PEMIIELHRFNPMQ-UHFFFAOYSA-M magnesium [2,6-di(propan-2-yl)phenyl]-(2-phenylethenyl)azanide bromide Chemical class C(C)(C)C1=C(N(C=CC2=CC=CC=C2)[Mg]Br)C(=CC=C1)C(C)C PEMIIELHRFNPMQ-UHFFFAOYSA-M 0.000 description 1
- CFZHOUYDAHXRLY-UHFFFAOYSA-N n-[chloro(dimethyl)silyl]-n-methylmethanamine Chemical compound CN(C)[Si](C)(C)Cl CFZHOUYDAHXRLY-UHFFFAOYSA-N 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 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 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FYGHSUNMUKGBRK-UHFFFAOYSA-N trimethylbenzene Natural products CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- 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
-
- 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
- C09K2211/104—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with other heteroatoms
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The invention provides a kind of double miscellaneous symmetrical aryl derivatives of five-membered ring, such compound has excellent optical activity, the big pi-conjugated system compound of specifically a kind of silicon bridge five-membered ring with N C C Si N skeletons.Its preparation method：Under the protection of nitrogen; with lithium diisopropyl amido (LDA) by the ketimide dehydrogenation of substituted base; equimolar magnesium bromide is added afterwards; obtain adding equimolar silane compound after magnesium salts and prepare compound; prepare amino-silicone bridge nitrogen-blending allyl lithium with LDA dehydrogenations again, finally with appropriate TiCl4Catalytic condition under obtain intramolecular reduction double miscellaneous symmetrical aryl derivative compounds of five-membered ring.Preparation method synthesis is simple, and materials are easy to get, are cheap, and yield is higher；This analog derivative has high optical physics property, good thermal stability, high fluorescent characteristic and high carrier mobility etc., available for electronic device and hole mobile material etc..
Description
Technical field
The present invention relates to double silicon bridge 5-membered ring compounds, the symmetrical aryl derivatives of specifically a kind of double miscellaneous five-membered rings and
Its preparation method and application.
Background technology
Double symmetrical aryl derivatives of miscellaneous five-membered ring are a kind of compounds with trapezoidal pi-electron conjugated structure, such chemical combination
Thing is a kind of good luminous organic material, available for light emitting diode, the neck such as transistor, and opticaly-pumpedsolidlaser
Domain.2000, Barton problems were combined into the symmetrical diphenyl compounds of a kind of silicon bridge, the five-membered ring symmetrical two of double methyl bridgings
Its fluorescence quantum yield of phenyl derivatives is very faint, and the symmetrical biphenyl derivatives of silicon bridge have preferable fluorescence quantum yield.
2007, Murakami problems were combined into a kind of silicon bridge terphenyl derivatives, had preferably electro；2014, Chinese section
Chemistry institute Xu's rainbow seminar of institute reports a kind of Coumarin benzene silicon derivative, have preferable optical physics property and from
Assembling characteristic.
The content of the invention
It is an object of the invention to provide a kind of double miscellaneous symmetrical aryl derivatives of five-membered ring and preparation method thereof, and such change
Compound is as a kind of application of luminous organic material.
A kind of double miscellaneous symmetrical aryl derivatives of five-membered ring provided by the invention, its structural formula are：
Wherein：
R1、R2And R3It is each independently selected from alkyl, aryl, alkaryl, aralkyl and the alcoxyl of hydrogen, 1-10 carbon atom
One kind in base；
It is preferred that R3Independently selected from hydrogen, methyl, ethyl, one kind in isopropyl and phenyl.
Present invention also offers the preparation method of a kind of double miscellaneous symmetrical aryl derivatives of five-membered ring, comprise the following steps：
(1) preparation of lithium salts：It is under acetone bath, the ketimine compound of substituted base and two is different under the protection of nitrogen
Propyl group amido lithium reaction with same mole, solvent is tetrahydrofuran, and after reacting 1-3 hours, it is equimolar to be cooled to -78 DEG C of additions again
Magnesium bromide, after solution is warming up to room temperature naturally, it is kept stirring for reacting 8-10 hours, obtains magnesium salts A tetrahydrofuran solution,
Under the protection of nitrogen, under ice-water bath, equimolar chlorosilane cpd is slowly added thereto, when solution is warming up to room naturally
After temperature, it is kept stirring for reacting 10-12 hours, the neutral compound B of oily is obtained by extraction with toluene；Then in the protection of nitrogen
Under, under ice-water bath, with equimolar butyl lithium lithiumation again, it is kept stirring for reacting 8-10 hours, is crystallized in tetrahydrofuran
To colourless amino-silicone bridge nitrogen-blending allyl lithium salt compound C；
(2) preparation of double symmetrical aryl derivatives of miscellaneous five-membered ring：Under the protection of nitrogen, under acetone bath, TiCl4Add
Enter into amino-silicone bridge nitrogen-blending allyl lithium salts C tetrahydrofuran solution, TiCl4Mol ratio with C is 1：1-4, when solution from
So it is warming up to after room temperature, is kept stirring for reacting 20-24 hours, vacuum is drained, and is added dichloromethane, filtering, filtrate is concentrated
Crystallization, obtain double miscellaneous symmetrical aryl derivative products D of five-membered ring.Specific synthetic route is as follows：
Advantages of the present invention and effect compared with prior art：The synthesis of such compound is raw materials used to be easy to get, price is low
Honest and clean, preparation method is simple, and yield is higher；The double miscellaneous symmetrical aryl derivatives of five-membered ring of this class, it is relatively stable in atmosphere, have
The heat endurance that high fluorescence quantum yield is become reconciled, available for electronic device and hole mobile material etc..
Brief description of the drawings
Fig. 1 is R1For isopropyl, R2For H, R3For Me five-membered ring D1 crystal structure figure；The benzene of unsubstituted group in figure
Ring forms the system of a conjugation with center system.
Fig. 2 is R1For ethyl, R2For H, R3For Me five-membered ring D2 crystal structure figure；The phenyl ring of unsubstituted group in figure
The system of a conjugation is formed with center system.
Fig. 3 is R1For methyl, R2For H, R3For Me five-membered ring D3 crystal structure figure；The phenyl ring of unsubstituted group in figure
The system of a conjugation is formed with center system.
Fig. 4 is R1For methyl, R2For methyl, R3For Me five-membered ring D4 crystal structure figure；The benzene of unsubstituted group in figure
Ring forms the system of a conjugation with center system.
Fig. 5 is R1For ethyl, R2For methyl, R3For Me five-membered ring D5 crystal structure figure；The benzene of unsubstituted group in figure
Ring forms the system of a conjugation with center system.
Fig. 6 is the symmetrical aryl compound D1-D4 of the double silicon bridges of double miscellaneous five-membered rings uv absorption spectra, and absorption spectra is in figure
Determined in ether solvent.
Fig. 7 is the symmetrical aryl compound D1-D4 of double double silicon bridges of miscellaneous five-membered ring fluorescent emission and exciting light spectrogram, is inhaled in figure
Spectrum is received to determine in ether solvent.
Embodiment
Only the embodiment that provides, these embodiments are not intended to limit the protection of the present invention to illustrate the invention below
Scope.
Embodiment 1
(1) preparation of lithium salts
Under the protection of nitrogen, under acetone bath, by lithium diisopropyl amido (0.21g, 2mmol) be added to N- phenethyls-
In the tetrahydrofuran solution of 2,6- diisopropyl benzene imines (0.56g, 2mmol), after reacting 3 hours, -78 DEG C are cooled to again and is added
Enter magnesium bromide (0.37g, 2mmol), after solution is warming up to room temperature naturally, be kept stirring for reaction 8 hours, vacuum is drained, just oneself
Alkane washs, and is recrystallized to give the tetrahydrofuran complex A1 of 2,6- diisopropyl-N- styryl anilino- magnesium bromides.In nitrogen
Protection under, under ice-water bath, dimethylamino dimethyl silicon chloride (0.3ml, 2mmol) is slowly added to A1 tetrahydrochysene furan
Mutter in solution, after solution is warming up to room temperature naturally, be kept stirring for reaction 6 hours, the N- (2- of oily are obtained by extraction with toluene
Dimethylamino dimethyl silicon substrate -1- styryls) -2,6-DIPA neutral compound B1.Then in the guarantor of nitrogen
Under shield, under acetone bath, with lithium diisopropyl amido (0.21g, 2mmol) lithiumation again, reaction 6 hours is kept stirring for, in tetrahydrochysene
Crystallization obtains colourless N- (2- dimethylamino dimethyl silicon substrate -1- styryls) -2,6-DIPA base lithium in furans
Salt complex C1；
Intermediate A 1, B1 and C1 yield and nuclear-magnetism, elemental analysis data are as follows：
A1:Colorless crystalline thing, yield 98%.1H NMR(300MHz C6D6):δ1.11(d,12H,CH(CH3)2),2.60–
2.64(m,2H,CH(CH3)2),4.08-4.10(d,2H,CH2),7.23–7.30(m,5H,Ph),7.38–7.41(m,3H,
Aryl).13C NMR(75MHz C6D6):δ24.44,26.57(CH(CH3)2),31.33(CH(CH3)2),96.45(CH2),
126.12(p-Ar),130.29(m-Ar),131.45(o-Ph),133.76(p-Ph),134.05(m-Ph),138.66(ipso-
), CPh 139.12 (ipso-CAr), 141.77 (ipso-CAr-N), 168.39 (N=C) Elemental Analysis theories:C, 63.83；
H,7.65；N, 2.66%. measured value：C,63.81；H,7.68；N,2.70.
B1：Light yellow oil, yield：97%.1H NMR(300MHz CDCl3):δ0.01(d,6H,Si(CH3)2),
1.08(s,2H,CH2),1.31-1.43(d,12H,CH(CH3)2),2.33-2.47(d,6H,N(CH3)2),2.99(m,2H,CH
(CH3)2),7.22-7.30(m,5H,Ph),7.59(s,2H,m-Ar),8.03(d,1H,p-Ar).
C1：Colorless crystalline thing, yield：98%.1H NMR(300MHz C6D6)δ0.05(d,6H,Si(CH3)2),0.67-
0.71(m,12H,CH(CH3)2),0.76-0.83(q,12H,3THF),2.25-2.26(d,6H,N(CH3)2),2.80(q,12H,
3THF),3.31-3.35(m,2H,CH(CH3)2),3.13-3.14(d,1H,CH),6.44-6.48(q,2H,o-Ph),6.53-
6.61(m,3H,m,p-Ph),6.68(d,1H,p-Ar),7.10-7.13(d,2H,m-Ar).13C NMR(75MHz C6D6)δ-
3.96(Si(CH3)2),23.85-24.58(CH3,iPr),26.03(CH2, THF), 28.38-29.45 (CH, iPr), 38.86 (N
(CH3)2),68.43(O-CH2,THF),73.36(CH),121.34(p-Ar),123.51(m-Ar),126.57(o-Ph),
127.44(p-Ph),129.37(m-Ph),143.09(ipso-CPh),146.35(ipso-CAr),152.14(ipso-CAr-N),
172.90 (N=C) Elemental Analysis theories：C,71.72；H,9.86；N, 4.65%. measured value：C,71.69；H,9.83；N,
4.64.
(2) the double miscellaneous symmetrical aryl derivatives D1 of five-membered ring of (2,6- diisopropyls) anilino- preparation：Schlenk bottles are taken out
Vacuum leads to N2After displacement three times, C1 (0.81g, 2mmol) and tetrahydrofuran 25ml is added, TiCl is added at -78 DEG C4
(0.23ml, 2mmol) stirring is lower to recover room temperature reaction 24 hours, and vacuum, which is drained, adds 50 milliliters of dichloromethane, filters, concentration,
N-hexane washs, and is crystallized in dichloromethane, obtains compound D1 0.54 gram of crocus bulk crystals, yield：81%.1H NMR
(300MHz CDCl3)δ0.12(s,12H,Si(CH3)2),1.04,1.10(d,24H,CH(CH3)2,3JHH=6.6Hz), 3.60
(sept,4H,CH(CH3)2,3JHH=6.9Hz), 6.83 (q, 2H, p-Ar), 6.92-6.95 (m, 4H, m, p-Ar), 7.06-7.16
(m,6H,p-Ph),7.31(m,4H,m-Ar).13C NMR(75MHz CDCl3)δ0.87(Si(CH3)2),23.69(CH3,iPr),
25.73,26.68(CH,iPr),115.48(C-C),122.02,125.42,127.22,140.87(Ph),128.56,
(146.93,147.37 Ar) 144.47 (C-Ph) Elemental Analysis theory：C44H56N2Si2:C,78.98；H,8.44；N,4.19.
Measured value：C,78.96；H,8.45；N, 4.18. crystal structure are shown in Fig. 1.
Embodiment 2
Initiation material is N- phenethyl -2,6- diethylbenzene imines, and remaining obtains (2,6- diethyl) benzene with embodiment 1
The double miscellaneous symmetrical aryl derivatives D2 of five-membered ring of amido 0.34 gram of yellow green bulk crystals, yield：56%, crystal structure is shown in Fig. 2.
Embodiment 3
Initiation material is N- phenethyl -2,6- dimethyl benzene imines, and remaining obtains (2,6- dimethyl) benzene with embodiment 1
The double miscellaneous symmetrical aryl derivatives D3 of five-membered ring of amido 0.40 gram of yellow green bulk crystals, yield：71%, crystal structure is shown in Fig. 3.
Embodiment 4
Initiation material is N- phenethyls -2,4, and 6- trimethylbenzene imines, remaining obtains (2,4,6- front threes with embodiment 1
Base) double miscellaneous symmetrical D40.38 grams of the aryl derivatives yellow green bulk crystals compounds of five-membered ring of anilino-, yield：65%, crystal
Structure is shown in Fig. 4.
Embodiment 5
Initiation material is N- phenethyl -2,6- diethyl 4- methylbenzene imines, and remaining obtains (2,6- diethyls with embodiment 1
Base -4- methyl) double miscellaneous symmetrical 0.49 gram of the aryl derivatives D5 yellow greens bulk crystals of five-membered ring of anilino-, yield：76%, crystal
Structure is shown in Fig. 5.
Embodiment 6
A certain amount of double miscellaneous symmetrical aryl derivatives D1-D4 of five-membered ring are dissolved in ether respectively, using ether as reference liquid,
Choose ultraviolet light absorption spectrum and fluorescent emission pole excitation spectrum that finite concentration is measured its compound, its absorption maximum data
Arrange as shown in table 1.
The symmetrical aryl derivatives D1-D4 of the miscellaneous five-membered ring of 1 pair, table optical physics property
In ether solvent, strong electronic vibration absorption spectra is all presented in all compounds, and we only list most herein
Big absorption value.
Claims (3)
1. a kind of double miscellaneous symmetrical aryl derivatives of five-membered ring, it is characterised in that structural formula is：
Wherein：
R1And R2It is each independently selected from the alkyl of hydrogen, 1-10 carbon atom；R3One kind in methyl, ethyl and isopropyl.
A kind of 2. preparation method of double miscellaneous symmetrical aryl derivatives of five-membered ring as claimed in claim 1, it is characterised in that including
Following steps：
(1) preparation of lithium salts：Under the protection of nitrogen, under acetone bath, by the ketimine compound and diisopropyl of substituted base
Amido lithium reaction with same mole, solvent are tetrahydrofuran, after reacting 1-3 hours, are cooled to -78 DEG C again and add equimolar bromination
Magnesium, after solution is warming up to room temperature naturally, it is kept stirring for reacting 8-10 hours, the tetrahydrofuran solution of magnesium salts is obtained, in nitrogen
Under the protection of gas, under ice-water bath, equimolar chlorosilane cpd is slowly added thereto, when solution be warming up to naturally room temperature with
Afterwards, it is kept stirring for reacting 10-12 hours, the neutral compound of oily is obtained by extraction with toluene；Then under the protection of nitrogen, ice
Under water-bath, with equimolar lithium diisopropyl amido lithiumation again, it is kept stirring for reacting 8-10 hours, is crystallized in tetrahydrofuran
Obtain colourless amino-silicone bridge nitrogen-blending allyl lithium；
(2) preparation of double symmetrical aryl derivatives of miscellaneous five-membered ring：Under the protection of nitrogen, under acetone bath, TiCl4It is added to
In the tetrahydrofuran solution of amino-silicone bridge nitrogen-blending allyl lithium, TiCl4Mol ratio with amino-silicone bridge nitrogen-blending allyl lithium is 1：
1-4, after solution is warming up to room temperature naturally, it is kept stirring for reacting 20-24 hours, vacuum is drained, and adds dichloromethane, mistake
Filter, filtrate condensing crystallizing is obtained into double miscellaneous symmetrical aryl derivatives of five-membered ring.
3. double miscellaneous symmetrical aryl derivatives of five-membered ring as claimed in claim 1 are used as luminous organic material.
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