CN102234264B - Synthesis method of N-[6-(8-benzyloxy quinolyl)-hexyl]carbazole - Google Patents
Synthesis method of N-[6-(8-benzyloxy quinolyl)-hexyl]carbazole Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title abstract description 5
- UPZJTYXTDMWDJS-UHFFFAOYSA-N 9-[6-(8-phenylmethoxyquinolin-2-yl)hexyl]carbazole Chemical compound C(C1=CC=CC=C1)OC=1C=CC=C2C=CC(=NC12)CCCCCCN1C2=CC=CC=C2C=2C=CC=CC12 UPZJTYXTDMWDJS-UHFFFAOYSA-N 0.000 title abstract 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 69
- LZYYBSWLPXPHAO-UHFFFAOYSA-N 5-bromo-8-phenylmethoxyquinoline Chemical compound C12=NC=CC=C2C(Br)=CC=C1OCC1=CC=CC=C1 LZYYBSWLPXPHAO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 115
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 114
- 238000009835 boiling Methods 0.000 claims description 69
- 239000000047 product Substances 0.000 claims description 64
- 239000000243 solution Substances 0.000 claims description 63
- 238000010025 steaming Methods 0.000 claims description 61
- 229960005419 nitrogen Drugs 0.000 claims description 60
- 229910052757 nitrogen Inorganic materials 0.000 claims description 55
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 52
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 48
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 35
- 239000012071 phase Substances 0.000 claims description 34
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 30
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 238000005485 electric heating Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 238000000605 extraction Methods 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 16
- 239000012065 filter cake Substances 0.000 claims description 16
- AAPFRICPXPVKAU-UHFFFAOYSA-N C(C1=CC=CC=C1)OC=1C=CC=C2C=CC(=NC12)CCCCCCC1=CC=CC=2C3=CC=CC=C3NC12.[N] Chemical compound C(C1=CC=CC=C1)OC=1C=CC=C2C=CC(=NC12)CCCCCCC1=CC=CC=2C3=CC=CC=C3NC12.[N] AAPFRICPXPVKAU-UHFFFAOYSA-N 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 15
- 235000017550 sodium carbonate Nutrition 0.000 claims description 15
- CUTSCJHLMGPBEJ-UHFFFAOYSA-N [N].CN(C)C=O Chemical compound [N].CN(C)C=O CUTSCJHLMGPBEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000000967 suction filtration Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- 125000004803 chlorobenzyl group Chemical group 0.000 claims description 13
- 238000004587 chromatography analysis Methods 0.000 claims description 13
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 9
- 229910000085 borane Inorganic materials 0.000 claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 9
- 230000005494 condensation Effects 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 9
- 229920000742 Cotton Polymers 0.000 claims description 8
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 239000000741 silica gel Substances 0.000 claims description 8
- 229910002027 silica gel Inorganic materials 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 7
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 7
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 5
- 238000002189 fluorescence spectrum Methods 0.000 claims description 5
- 239000011368 organic material Substances 0.000 claims description 5
- 238000000103 photoluminescence spectrum Methods 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 238000004773 frontier orbital Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 235000007516 Chrysanthemum Nutrition 0.000 claims description 2
- 244000189548 Chrysanthemum x morifolium Species 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 claims description 2
- MGARILXXHSLKKA-UHFFFAOYSA-N C(C1=CC=CC=C1)OC=1C=CC=C2C=CC(=NC12)CCCCCCC1=CC=CC=2C3=CC=CC=C3NC12 Chemical compound C(C1=CC=CC=C1)OC=1C=CC=C2C=CC(=NC12)CCCCCCC1=CC=CC=2C3=CC=CC=C3NC12 MGARILXXHSLKKA-UHFFFAOYSA-N 0.000 claims 1
- 230000005284 excitation Effects 0.000 abstract description 5
- 230000003287 optical effect Effects 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- HFNNZEMVTJAKRC-UHFFFAOYSA-N 9-(6-bromohexyl)carbazole Chemical compound C1=CC=C2N(CCCCCCBr)C3=CC=CC=C3C2=C1 HFNNZEMVTJAKRC-UHFFFAOYSA-N 0.000 abstract 1
- 241001025261 Neoraja caerulea Species 0.000 abstract 1
- ZMIXHUMHTRANEM-UHFFFAOYSA-N [Na].BrC1=C2C=CC=NC2=C(C=C1)O Chemical compound [Na].BrC1=C2C=CC=NC2=C(C=C1)O ZMIXHUMHTRANEM-UHFFFAOYSA-N 0.000 abstract 1
- 230000007704 transition Effects 0.000 description 6
- 238000012546 transfer Methods 0.000 description 5
- FPFKXDKOMIEEPB-UHFFFAOYSA-N 8-phenylmethoxyquinoline Chemical group C=1C=CC2=CC=CN=C2C=1OCC1=CC=CC=C1 FPFKXDKOMIEEPB-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 150000001716 carbazoles Chemical class 0.000 description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- -1 5-bromo-oxine Chemical compound 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 230000004001 molecular interaction Effects 0.000 description 1
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- Indole Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention relates to a synthesis method of N-[6-(8-benzyloxy quinolyl)-hexyl]carbazole. The synthesis method is characterized by firstly synthesizing N-(6-bromohexyl)carbazole, 5-bromo-8-hydroxyquinoline sodium, 5-bromo-8-benzyloxy quinoline and 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-8-benzyloxy quinoline from carbazole and other organic substances used as raw materials and finally synthesizing N-[6-(8-benzyloxy quinolyl)-hexyl]carbazole yellow oily product (CZBQ product). The obtained CZBQ product is an organic electroluminescent material which has an optical band gap of 3.02 eV, can emit blue light under the excitation of ultraviolet rays with a wavelength of 365 nm, has excellent solubility and film-forming properties and good light emitting performance, and is suitable for the wet preparation of a blue-ray OLED (organic light-emitting diode). The synthesis method has the advantages of advanced process and reasonable proportioning, and is precise, accurate and strict; and the obtained product has a purity of 96.8% and a yield of 93.2%.
Description
Technical field
The present invention relates to the synthesis method of a kind of nitrogen-[6-(8-benzyloxy quinolyl)-hexyl] carbazole, belong to the preparation of organic small molecule material and the technical field of application.
Background technology
Carbazole has larger rigid planar structure and reaches larger π-electron conjugated system and the stronger interior transfer transport characteristic of molecule, it is superior hole mobile material, be widely used in preparing organic molecule and polymer luminescent material, 3 of carbazole, 6,9 easy binding functional groups form multiple carbazole derivative, for example the H on the N atom of carbazole can be replaced by the alkyl with bromine atoms, to strengthen the solvability of carbazole derivative; Oxine and derivative thereof have good thermostability and luminosity, are good electron transport materials, often are used to fine chemistry industry dyestuff and pharmaceutical intermediate.
Binding hexyl chain on 9 nitrogen-atoms of carbazole, the end of the chain are introduced 8-benzyloxy quinoline group, can synthesize Nitrogen in Products-[6-(8-benzyloxy quinolyl)-hexyl] carbazole, i.e. C
ZThe BQ product, this product principle of design is: the end at a molecule is introduced cavity transmission group carbazole, the other end binding electric transmission group 8-benzyloxy quinoline; The introducing of alkyl chain has been avoided by the charge transfer of carbazole to the quinoline group, and has increased the solvability of product, makes the unimpeded transfer that has realized energy in the molecule; Product C
ZThe BQ film-forming properties is good, is applicable to the wet methods such as spray ink Printing, spin coating and is prepared with organic electroluminescence devices.
C
ZThe synthetic of BQ product is the technological process of a complexity, and synthetic difficulty is larger, and its product purity, yield, luminescent properties all need further research.
Summary of the invention
Goal of the invention
The objective of the invention is for the background technology situation; adopt carbazole, Tetrabutyl amonium bromide, potassium hydroxide, 5-bromo-oxine, sodium hydroxide, chloro benzyl, 4; 4; 5; 5-four bases-1; 3; 2-oxa-borine, tetrakis triphenylphosphine palladium are raw material; by building-up reactions in four-hole boiling flask; in heating, stirring, water cycle condensation, protection of inert gas, column chromatography purification, recrystallization purification, vacuum-drying; make nitrogen-[6-(8-benzyloxy quinolyl)-hexyl] carbazole, with purity and the production yield rate that increases substantially product.
Technical scheme
The chemical substance material that the present invention uses is:
Raw material:
Carbazole: C
6H
12N 5.0g ± 0.001g
1,6-dibromo-hexane: C
6H
12Br 17.5ml ± 0.001ml
Tetrabutyl amonium bromide: C
16H
36BrN 0.096g ± 0.0001g
Potassium hydroxide: KOH 16.8g ± 0.01g
5-bromo-oxine: C
9H
6BrNO 8.96g ± 0.001g
Sodium hydroxide: NaOH 2.0g ± 0.001g
Chloro benzyl: C
7H
7Cl 6.0ml ± 0.001ml
4,4,5,5-tetramethyl--1,3,2-oxa-borine: C
6H
13BO
22.4ml ± 0.001ml
Tetrakis triphenylphosphine palladium: (PPh
3)
4Pd (0) 1.0g ± 0.0001g
Yellow soda ash: Na
2CO
35.088g ± 0.0001g
Solvent:
Tetrahydrofuran (THF): C
4H
8O 150ml ± 10ml
Ethanol: C
2H
5OH 200ml ± 10ml
Methylene dichloride: CH
2Cl
2100ml ± 10ml
Sherwood oil: 3000ml ± 50ml
Nitrogen, nitrogen-dimethyl formamide: C
3H
7NO 70ml ± 1ml
Isopropyl ether: C
6H
4O 15ml ± 1ml
Triethylamine: Et
3N 15ml ± 0.1ml
Ether: C
4H
10O 1000ml ± 20ml
Benzene: C
6H
6100ml ± 10ml
Deionized water: H
2O 4000ml ± 50ml
Mixture of ice and water: H
2O 500ml ± 10ml
Silica gel: 200-300 order 1500g ± 10g
Absorbent cotton: 5.0g ± 1g
Nitrogen: N
210000cm
3± 100cm
3
The preparation synthetic method is as follows:
(1) synthetic nitrogen-(6-bromine hexyl) carbazole
1. synthesize in four-hole boiling flask and carry out, four-hole boiling flask is placed on the electric mantle, on the four-hole boiling flask by left-to-right nitrogen tube, dropping funnel, agitator, the water cycle prolong of inserting successively;
2. prepare potassium hydroxide aqueous solution
Potassium hydroxide 16.8g ± 0.001g is placed beaker, add deionized water 18.8ml ± 0.001ml, stir 5min with glass stick, become: the aqueous solution of the potassium hydroxide of 16mol/L;
3. in four-hole boiling flask, add:
Carbazole: 5g ± 0.001g
1,6-dibromo-hexane: 17.5ml ± 0.001ml
Tetrabutyl amonium bromide: 0.096g ± 0.0001g
Tetrahydrofuran (THF): 30ml ± 1ml
4. open nitrogen tube, in four-hole boiling flask, input nitrogen, input rate 20cm
3/ min;
5. open water circulating condensing pipe and production well;
6. open electric mantle, the heating four-hole boiling flask, temperature is warming up to 90 ℃ ± 2 ℃ gradually by 25 ℃;
7. turn on agitator is mixed the chemical substance in the four-hole boiling flask;
8. potassium hydroxide aqueous solution is placed dropping funnel, and drip rate of addition 1.2ml/min;
The limit heating, the limit drips, and stir on the limit, limit input nitrogen, reactant gases, reaction times 240min ± 5min are discharged in the limit;
Reaction formula is:
9. after reaction finishes, close electric mantle, agitator, water cycle prolong, nitrogengas cylinder, make it naturally cool to 25 ℃ with four-hole boiling flask;
Become in the four-hole boiling flask after the reaction: carbazole+1,6-dibromo-hexane+Tetrabutyl amonium bromide+tetrahydrofuran (THF)+potassium hydroxide aqueous solution, that is: hexa-atomic mixing solutions;
10. use the hexa-atomic mixing solutions of dichloromethane extraction
Hexa-atomic mixing solutions is poured in the separating funnel, then added oil phase methylene chloride 20ml, then place on the vibration ware, vibration mixes 10min, becomes: water+oil phase mixed solution, leave standstill 5min, and water and separation of oil are collected oil phase liquid;
Oil phase liquid is placed separating funnel, add deionized water 100ml, shake the vibration separating funnel, oil phase liquid is fully mixed with water, become: water+oil phase mixed solution, leave standstill 5min, water and separation of oil are collected oil phase liquid;
The oil phase liquid washing repeats 3 times;
Oil phase liquid is added in the single port flask, then place vacuum to revolve on the steaming machine and revolve steaming, revolve and steam 40 ℃ of temperature, vacuum tightness 0.08Pa revolves steaming time 30min;
Naturally cool at random 25 ℃ after revolving steaming;
Revolve and steam rear one-tenth: yellow oil product
The dress post: the 300g dry silica gel is placed beaker, add sherwood oil 300ml, stir with glass stick, become mixed solution, then add in the chromatography column, top adds absorbent cotton 0.5g;
Drip washing: yellow oil product is added in the chromatography column, carry out drip washing with sherwood oil 300ml;
Collect: the yellow petroleum ether solution after the drip washing;
Get after revolving steaming: yellow-white oily product
Recrystallization is purified and is carried out in the single port Florence flask, yellow-white oily product is placed the single port Florence flask, the single port Florence flask is placed on the electric heating agitator, add ethanol 15ml, access water cycle prolong, 90 ℃ ± 2 ℃ of Heating temperatures, 120min is stirred in vibration, then while hot solution is placed on the chrysanthemum shape filter paper on the filter flask and filters, the filtering insolubles, collect solution, after the solution cooling, separate out white needle-like crystals;
White needle-like crystals is: nitrogen-(6-bromine hexyl) carbazole
(2) synthetic 5-bromo-oxine sodium
1. prepare aqueous sodium hydroxide solution
Sodium hydroxide 2g ± 0.001g is placed beaker, add deionized water 10ml ± 0.001ml, stir 5min, become: the aqueous sodium hydroxide solution of 5mol/L;
2. synthesize in four-hole boiling flask and carry out, four-hole boiling flask is placed on the electric heating agitator, on four-hole boiling flask, insert successively from left to right thermometer, dropping funnel, agitator, water cycle prolong;
3. take by weighing: 5-bromo-oxine 8.96g ± 0.001g
Measure: ethanol 60ml ± 1ml
Add in the four-hole boiling flask;
4. open the electric heating agitator, the water cycle prolong, temperature rises to 70 ℃ ± 2 ℃;
5. aqueous sodium hydroxide solution is added dropping funnel and dropping, rate of addition 1.2ml/min, the limit vibration is stirred, limit water cycle condensation, time 60min, yellowly mixing solutions in the four-hole boiling flask, that is: yellow 5-bromo-oxine+ethanol+sodium hydroxide+deionized water quaternary mixing solutions;
Reaction formula is:
Building-up reactions is closed electric heating agitator, water cycle prolong after finishing, and makes it naturally cool to 25 ℃ with bottle;
6. suction filtration
Yellow quaternary mixing solutions is placed Büchner funnel on the filter flask, carry out suction filtration with two layers of fast qualitative filter paper, retain the product filter cake on the filter paper, waste liquid is evacuated in the filter flask;
7. vacuum-drying
The product filter cake is placed on the quartz container, then place vacuum drying oven to carry out drying, 40 ℃ ± 2 ℃ of drying temperatures, vacuum tightness 0.09Pa, time of drying, 1440min got after the drying: buff powder, that is: 5-bromo-oxine sodium;
(3) synthetic 5-bromo-8-benzyloxy quinoline
1. prepare chloro benzyl+nitrogen, nitrogen-dimethyl formamide mixing solutions
Chloro benzyl 5.8ml ± 0.001ml is placed beaker, add nitrogen, nitrogen-dimethyl formamide 15ml ± 1ml stirs 5min, becomes: chloro benzyl+nitrogen, nitrogen-dimethyl formamide Binary Mixtures;
2. synthesize and in four-hole boiling flask, carry out, four-hole boiling flask is placed on the electric heating agitator, on four-hole boiling flask, insert successively from left to right nitrogen tube, dropping funnel, extraction pipe, water cycle prolong;
3. open the extraction pipe 5min that bleeds, then logical nitrogen 5min substitutes gas and repeats 3 times;
4. take by weighing: 5-bromo-oxine sodium 9.84g ± 0.001g
Measure: nitrogen, nitrogen-dimethyl formamide 40ml ± 1ml
Add in the four-hole boiling flask;
5. open the electric heating agitator, be heated to 90 ℃ ± 2 ℃, stir, open water circulating condensing pipe carries out the water cycle condensation;
6. with chloro benzyl+nitrogen, nitrogen-dimethyl formamide Binary Mixtures adds in the dropping funnel, and drips rate of addition 1.2ml/min;
Stir on limit heating, limit, the limit drips, limit water cycle condensation, and time 240min becomes reaction soln, that is: chloro benzyl+nitrogen, nitrogen-dimethyl formamide+5-bromo-oxine sodium ternary mixing solutions;
Reaction formula is as follows
7. prepare frozen water
Deionized water 200ml is placed beaker, then place refrigerator, make deionized water be down to 0 ℃ ± 1 ℃ by 25 ℃, become frozen water;
8. the ternary mixing solutions is added while hot in 0 ℃ the frozen water, stir 20min, have pale solid to separate out in the whipping process, become: the canescence mixture of ice and water;
9. suction filtration
The canescence mixture of ice and water is placed the Büchner funnel on filter flask top, carry out suction filtration with two layers of fast qualitative filter paper, retain the product filter cake on the filter paper, waste liquid is evacuated in the filter flask;
10. deionized water wash, filtration
The product filter cake is placed beaker, adds deionized water 100ml, agitator treating 10min, then at filter flask with two layers of fast qualitative filter paper filtering;
Deionized water wash, filtration repeat three times;
The product filter cake is placed beaker, add isopropyl ether 10ml, agitator treating 10min: filter cake+isopropyl ether mixed solution;
Mixed solution is placed the Büchner funnel of filter flask, carry out suction filtration with two layers of fast qualitative filter paper, retain the product filter cake on the filter paper, waste liquid is evacuated in the filter flask;
The product filter cake is placed quartz container, then places vacuum drying oven dry, vacuum tightness 0.09Pa, 40 ℃ of drying temperatures, time of drying 1440min;
After the drying: white powder, that is: 5-bromo-8-benzyloxy quinoline;
(4) synthetic 5-(4,4,5,5-tetramethyl--1,3,2-oxa-borine-two base)-8-benzyloxy quinoline
1. prepare in four-hole boiling flask and carry out, four-hole boiling flask is placed on the electric heating agitator, extraction pipe, nitrogen tube, dropping funnel, water cycle prolong are set on four-hole boiling flask from left to right;
2. extract air 5min in the four-hole boiling flask, then pass into nitrogen 5min, substitute gas and repeat three times;
3. take by weighing: 5-bromo-8-benzyloxy quinoline 4.713g ± 0.001g
Measure: triethylamine 15ml ± 1ml
Measure: tetrahydrofuran (THF) 75ml ± 1ml
Take by weighing catalyzer: tetrakis triphenylphosphine palladium 0.52g ± 0.0001g
Add in the four-hole boiling flask;
4. open the electric heating agitator, be warming up to 70 ℃ ± 2 ℃;
Open water circulating condensing pipe carries out the water circulation condensation;
Agitator stirs 10min;
5. add 4,4,5,5-tetramethyl--1,3,2-oxa-borine 2.4ml ± 0.001ml by dropping funnel fast;
Continue to stir 1440min;
To carry out chemical reaction, reaction formula is as follows:
6. reaction finishes, and closes electric heating agitator, water cycle prolong, makes it be cooled to 25 ℃ with bottle;
Become after the reaction: 5-bromo-8-benzyloxy quinoline+triethylamine+tetrahydrofuran (THF)+tetrakis triphenylphosphine palladium+ 4,4,5,5-tetramethyl--1,3, five yuan of mixing solutionss of 2-oxa-borine;
7. dilute, remove by filter catalyzer with ether
Ether 100ml is added in the four-hole boiling flask by dropping funnel, then insert and turn on agitator, stir 10min, become: hexa-atomic dilution mixing solutions;
Hexa-atomic dilution mixing solutions is placed the Büchner funnel of filter flask, with two layers of fast qualitative filter paper suction filtration, retain the catalyzer tetrakis triphenylphosphine palladium on the filter paper, and remove;
Reaction soln is: 5-bromo-8-benzyloxy quinoline+triethylamine+tetrahydrofuran (THF)+4,4,5,5-tetramethyl--1,3,2-oxa-borine+ether five elementary reaction solution;
8. vacuum is revolved steaming, removes organic solvent
Five elementary reaction solution are placed the single port flask, then place vacuum to revolve on the steaming machine and revolve steaming, remove organic solvent, vacuum tightness 0.08Pa revolves and steams 40 ℃ of temperature, revolves steaming time 30min;
Get after revolving steaming: yellow oil product;
9. column chromatography is purified
The dress post: the 300g dry silica gel is placed beaker, add ether 300ml, stir into mixing solutions with agitator, then add in the chromatography column, top adds absorbent cotton 0.5g;
Drip washing: yellow oil product is added in the chromatography column, carry out drip washing with ether 500ml;
Collect: the yellow diethyl ether solution after the drip washing;
10. vacuum is revolved steaming, removes ether
Yellow diethyl ether solution after the drip washing is placed the single port flask, then place vacuum to revolve on the steaming machine and revolve steaming, vacuum tightness 0.08Pa revolves and steams 40 ℃ of temperature, revolves steaming time 60min;
Get after revolving steaming: the white powder product
That is: 5-(4,4,5,5-tetramethyl--1,3,2-oxa-borine-two base)-8-benzyloxy quinoline
(5) synthetic nitrogen-[6-(8-benzyloxy quinolyl)-hexyl] carbazole
1. synthesize in four-hole boiling flask and carry out, four-hole boiling flask is placed on the electric mantle, electric mantle is placed on the electric heating agitator, on four-hole boiling flask, insert successively from left to right extraction pipe, nitrogen tube, dropping funnel, water cycle prolong;
2. prepare aqueous sodium carbonate
With yellow soda ash 5.088g ± 0.001g, deionized water 24ml ± 0.01ml, place beaker, stir, become: aqueous sodium carbonate, concentration are 2mol/L;
3. open extraction pipe, extract air 5min in the bottle, then be filled with nitrogen 5min, substitute gas and repeat three times;
4. take by weighing: 5-(4,4,5,5-tetramethyl--1,3,2-oxa-borine-two base)-8-benzyloxy quinoline 1.588g ± 0.001g
Take by weighing: nitrogen-(6-bromine hexyl) carbazole 1.32g ± 0.001g
Take by weighing: tetrakis triphenylphosphine palladium 0.0693g ± 0.0001g
Measure: ethanol 4ml ± 0.001ml
Measure: benzene 20ml ± 1ml
Add in the four-hole boiling flask;
5. open the electric heating agitator, stir ware, open water circulating condensing pipe, temperature rises to 90 ℃ ± 2 ℃, stirs 10min;
6. aqueous sodium carbonate 24ml is added in the dropping funnel, in bottle, drip rate of addition 1ml/min;
The limit drips, stir on the limit, heat on the limit, limit water cycle condensing reflux, time 1440min;
To carry out chemical reaction, reaction formula is as follows:
7. after reaction finishes, close the electric heating agitator, stir ware, water cycle prolong, make it be cooled to 25 ℃ with bottle, become in the four-hole boiling flask: 5-(4,4,5,5-tetramethyl--1,3,2-oxa-borine-two base)-8-benzyloxy quinoline+nitrogen-(6-bromine hexyl) hexa-atomic mixing solutions of carbazole+tetrakis triphenylphosphine palladium+ethanol+yellow soda ash+deionized water;
8. benzene extracts secondary
Hexa-atomic mixing solutions is placed separating funnel, add benzene 20ml, vibration mixes 5min, leaves standstill, and water is lower, and oil phase is removed aqueous phase solution upper, retains oil phase liquid, and collects;
The benzene extraction repeats secondary;
9. deionized water wash, separating funnel separates
Oil phase liquid is placed separating funnel, add deionized water 100ml, vibration mixes 5min, makes water, separation of oil, and water is lower, and oil phase is removed water upper, retains oil phase;
10. vacuum is revolved steaming, removes organic solvent
Oil-phase solution is placed the single port flask, place vacuum to revolve steaming machine inward turning and steam, vacuum tightness 0.08Pa revolves and steams 40 ℃ of temperature, revolves steaming time 30min;
Get after revolving steaming: the yellow oily crude product
The dress post: the 300g dry silica gel is placed beaker, add sherwood oil 300ml, stir into mixing solutions with glass stick, then add in the chromatography column, top adds absorbent cotton 0.5g;
Drip washing: yellow oil product is added in the chromatography column, carry out drip washing with sherwood oil 500ml;
Collect: the yellow petroleum ether solution after the drip washing;
After the purification: oil phase crude product+sherwood oil mixed solution;
Mixed solution is placed beaker, then place vacuum to revolve on the steaming machine and revolve steaming, revolve the steaming temperature 50 C, vacuum tightness 0.08Pa revolves steaming time 60min, revolve after the steaming: yellow oil product;
The yellow oil product that to revolve after the steaming places loft drier, and vacuum tightness is 0.09Pa, 40 ℃ of drying temperatures, time of drying 1440min;
It is end product after dry: yellow oil product
That is: nitrogen-[6-(8-benzyloxy quinolyl)-hexyl] carbazole
That is: C
ZThe BQ yellow oil product
(6) detect, analyze, characterize
Synthetic yellow oil product is detected analysis and sign;
To C
ZThe molecular configuration of BQ yellow oil product is analyzed;
To C
ZThe frontier molecular orbitals of BQ is analyzed;
To C
ZThe ultraviolet-visible spectrum of BQ is analyzed;
To C
ZThe fluorescence spectrum of BQ is analyzed;
To C
ZThe photoluminescence spectra of BQ is analyzed;
Conclusion: Nitrogen in Products-[6-(8-benzyloxy quinolyl)-hexyl] carbazole is yellow oily;
Nitrogen in Products-[6-(8-benzyloxy quinolyl)-hexyl] carbazole is electroluminescent organic material, blue light-emitting;
(7) product stores
Synthetic yellow oil product is placed brown transparent Glass Containers, and airtight lucifuge stores, and moistureproof, sun-proof, anti-acid-alkali salt corrosion, 20 ℃ ± 2 ℃ of storing temps, relative humidity≤10%.
Described nitrogen-[6-(8-benzyloxy quinolyl)-hexyl] carbazole molecular configuration is: shown in Figure 2.
Described nitrogen-[6-(8-benzyloxy quinolyl)-hexyl] its frontier molecular orbitals of carbazole is: shown in Figure 3
Described nitrogen-[6-(8-benzyloxy quinolyl)-hexyl] carbazole uv-visible absorption spectra is: the absorption peak of nitrogen-[6-(8-benzyloxy quinolyl)-hexyl] carbazole 237nm is corresponding to the π-π of phenyl ring
*Transition, the absorption peak that is arranged in 293nm corresponding to carbazole group by the transition of electron of phenyl ring to pyrrole ring.
Described nitrogen-[6-(8-benzyloxy quinolyl)-hexyl] carbazole, fluorescence spectrum is: the fluorescence excitation peak position is in the 359nm place, and fluorescence emission peak is positioned at the 408nm place, is blue emission.
Described nitrogen-[6-(8-benzyloxy quinolyl)-hexyl] carbazole, photoluminescence spectra is: under the ultraviolet excitation of wavelength 365nm, the maximum emission wavelength of nitrogen-[6-(8-benzyloxy quinolyl)-hexyl] carbazole is 468nm, belongs to blue wave band, blue light-emitting.
Beneficial effect
The present invention compares with background technology has obvious advance, as raw material take organic substances such as carbazoles, elder generation's synthetic nitrogen-(6-bromine hexyl) carbazole, 5-bromo-oxine sodium, 5-bromo-8-benzyloxy quinoline, 5-(4,4,5,5-tetramethyl--1,3,2-oxa-borine-two base)-and 8-benzyloxy quinoline, final synthetic nitrogen-[6-(8-benzyloxy quinolyl)-hexyl] carbazole, be yellow oil product, i.e. C
ZThe BQ product, be electroluminescent organic material, its optical band gap is 3.02eV, be that its maximum emission wavelength is 468nm under the ultraviolet excitation of 365nm at wavelength, belonging to blue wave band, is a kind of electroluminescent organic material of blue light-emitting, and this product has good solvability and film-forming properties, be applicable to wet method and prepare blue light OLED, luminous efficiency is high, can be dissolved in multiple organic solvent, matches, good film-forming property, this synthetic method craft is advanced, reasonable ratio, accurately, accurately, tightly, product purity reaches 96.8%, and production yield rate reaches 93.2%.
Fig. 1 is C
ZBQ end product synthetic state figure
Fig. 2 is C
ZBQ product molecular configuration figure
Description of drawings
Fig. 3 is C
ZThe frontier molecular orbitals figure of BQ
Fig. 4 is C
ZThe uv-visible absorption spectra figure of BQ
Fig. 5 is C
ZThe fluorescence spectrum figure of BQ
Fig. 6 is C
ZThe photoluminescence spectra figure of BQ
Shown in the figure, list of numerals is as follows:
1, electric heating agitator, 2, pilot lamp, 3, trip switch, 4, stir ware, 5, thermometer, 6, four-hole boiling flask, 7, the water cycle prolong, 8, the air outlet, 9, water-in, 10, water outlet, 11, dropping funnel, 12, control valve, 13, nitrogen tube, 14, nitrogen valve, 15, nitrogengas cylinder, 16, extraction pipe, 17, extraction valve, 18, off-gas pump, 19, mixing solutions, 20, aqueous sodium carbonate, 21, electric mantle, 22, nitrogen.
Below in conjunction with accompanying drawing the present invention is done further proof:
Shown in Figure 1, be C
ZThe BQ end product prepares state graph, and it is correct that want each position, according to quantity proportioning, according to the order of sequence operation.
Embodiment
Synthetic required chemicals material is to determine by the scope that sets in advance, with gram, milliliter, centimetre
3, minute be measure unit.
Building-up process is the chemical reaction process of a complexity, has used multiple organic and inorganic material and chemicals, will strictly distinguish in synthetic, weighs, strict period, temperature, processing step.
Four-hole boiling flask, container, beaker, water cycle prolong, chromatography column, separating funnel, dropping funnel, the vacuum that preparation is used revolved steaming machine, loft drier, filter flask etc. will keep clean, must not have impurity to get involved, in order to avoid generate by product.
C
ZThe preparation of BQ end product is carried out at four-hole boiling flask, control panel at electric heating agitator (1) is provided with pilot lamp (2), trip switch 3, stir ware 4, thermometer (5), be electric mantle (21) on the top of electric heating agitator (1), be four-hole boiling flask (6) at electric mantle (21), be provided with successively from left to right extraction pipe (16) on four-hole boiling flask (6) top, nitrogen tube (13), dropping funnel (11) and control valve (12), water cycle prolong (7) and air outlet (8), water-in (9), water outlet (10); Be hexa-atomic mixing solutions (19) in four-hole boiling flask (6); Be aqueous sodium carbonate (20) in dropping funnel (11); Extraction pipe (16) connects off-gas pump (18), and is controlled by extraction valve (17); Nitrogen tube (13) connects nitrogengas cylinder (15), and is controlled by nitrogen valve (14).
Shown in Figure 2, be C
ZBQ product molecular configuration figure, among the figure as can be known: Nitrogen in Products-[6-(8-benzyloxy quinolyl)-hexyl] carbazole is the nonplanar structure organic molecule, carbazole group and 8-benzyloxy quinoline group are distributed on the different planes, the intervention of aliphatic chain has destroyed the conjugacy of whole molecule, thereby has limited the transfer transport by carbazole hoop quinoline ring.
Shown in Figure 3, be C
ZBQ product front molecule trajectory diagram, among the figure as can be known: on Nitrogen in Products-[6-(8-benzyloxy quinolyl)-hexyl] highest occupied molecular orbital(HOMO) of carbazole and the phenol ring that lowest unoccupied molecular orbital is distributed in respectively oxine and pyridine ring on, work as C
ZAfter BQ is excited, occured corresponding to the transfer transport by phenol hoop pyridine ring.
Shown in Figure 4, be C
ZBQ product uv-visible absorption spectroscopy figure, among the figure as can be known: the absorption peak of Nitrogen in Products-[6-(8-benzyloxy quinolyl)-hexyl] carbazole 237nm is corresponding to the π-π of phenyl ring
*Transition, the absorption peak that is arranged in 293nm corresponding to carbazole group by the transition of electron of phenyl ring to pyrrole ring.
Shown in Figure 5, be C
ZBQ product fluorescence spectrum figure, among the figure as can be known: the fluorescence emission peak of Nitrogen in Products-[6-(8-benzyloxy quinolyl)-hexyl] carbazole is positioned at the 408nm place, is blue emission, its luminescent spectrum and C
ZThe emission wavelength that the emission wavelength that BQ calculates by the electrochemical data that cyclic voltammetry obtains and theoretical modeling obtain is consistent.
Shown in Figure 6, be C
ZThe photoluminescence spectra of BQ product, among the figure as can be known: product C
ZBQ is under the ultraviolet excitation of 365nm at wavelength, its maximum emission wavelength is 468nm, belongs to blue wave band, blue light-emitting, relative its fluorescent emission red shift of wavelength, be owing to molecule increase in density when the film attitude, molecular interaction is strengthened, and has formed molecule aggregates, the molecular transition dipole shows as " head to head " linear array, form " J-aggregate ", thereby occured to the transition of low excited state energy level, thereby in spectrum, show as the red shift of peak position.
Claims (2)
1. the synthetic method of nitrogen-[6-(8-benzyloxy quinolyl)-hexyl] carbazole, it is characterized in that: the chemical substance material of use is:
Raw material:
Carbazole: C
6H
12N 5.0g ± 0.001g
1,6-dibromo-hexane: C
6H
12Br 17.5ml ± 0.001ml
Tetrabutyl amonium bromide: C
16H
36BrN 0.096g ± 0.0001g
Potassium hydroxide: KOH 16.8g ± 0.01g
5-bromo-oxine: C
9H
6BrNO 8.96g ± 0.001g
Sodium hydroxide: NaOH 2.0g ± 0.001g
Chloro benzyl: C
7H
7Cl 6.0ml ± 0.001ml
4,4,5,5-tetramethyl--1,3,2-oxa-borine: C
6H
13BO
22.4ml ± 0.001ml
Tetrakis triphenylphosphine palladium: (PPh
3)
4Pd (0) 1.0g ± 0.0001g
Yellow soda ash: Na
2CO
35.088g ± 0.0001g
Solvent:
Tetrahydrofuran (THF): C
4H
8O 150ml ± 10ml
Ethanol: C
2H
5OH 200ml ± 10ml
Methylene dichloride: CH
2Cl
2100ml ± 10ml
Sherwood oil: 3000ml ± 50ml
Nitrogen, nitrogen-dimethyl formamide: C
3H
7NO 70ml ± 1ml
Isopropyl ether: C
6H
4O 15ml ± 1ml
Triethylamine: Et
3N 15ml ± 0.1ml
Ether: C
4H
10O 1000ml ± 20ml
Benzene: C
6H
6100ml ± 10ml
Deionized water: H
2O 4000ml ± 50ml
Mixture of ice and water: H
2O 500ml ± 10ml
Silica gel: 200-300 order 1500g ± 10g
Absorbent cotton: 5.0g ± 1g
Nitrogen: N
210000cm
3± 100 cm
3
The preparation synthetic method is as follows:
(1) synthetic nitrogen-(6-bromine hexyl) carbazole
1. synthesize in four-hole boiling flask and carry out, four-hole boiling flask is placed on the electric mantle, on the four-hole boiling flask by left-to-right nitrogen tube, dropping funnel, agitator, the water cycle prolong of inserting successively;
2. prepare potassium hydroxide aqueous solution
Potassium hydroxide 16.8g ± 0.001g is placed beaker, add deionized water 18.8ml ± 0.001ml, stir 5min with glass stick, become: the aqueous solution of the potassium hydroxide of 16mol/L;
3. in four-hole boiling flask, add:
Carbazole: 5g ± 0.001g
1,6-dibromo-hexane: 17.5ml ± 0.001ml
Tetrabutyl amonium bromide: 0.096g ± 0.0001g
Tetrahydrofuran (THF): 30ml ± 1ml
4. open nitrogen tube, in four-hole boiling flask, input nitrogen, input rate 20cm
3/ min;
5. open water circulating condensing pipe and production well;
6. open electric mantle, the heating four-hole boiling flask, temperature is warming up to 90 ℃ ± 2 ℃ gradually by 25 ℃;
7. turn on agitator is mixed the chemical substance in the four-hole boiling flask;
8. potassium hydroxide aqueous solution is placed dropping funnel, and drip rate of addition 1.2ml/min;
The limit heating, the limit drips, and stir on the limit, limit input nitrogen, reactant gases, reaction times 240min ± 5min are discharged in the limit;
Reaction formula is:
9. after reaction finishes, close electric mantle, agitator, water cycle prolong, nitrogengas cylinder, make it naturally cool to 25 ℃ with four-hole boiling flask;
Become in the four-hole boiling flask after the reaction: carbazole+1,6-dibromo-hexane+Tetrabutyl amonium bromide+tetrahydrofuran (THF)+potassium hydroxide aqueous solution, that is: hexa-atomic mixing solutions;
10. use the hexa-atomic mixing solutions of dichloromethane extraction
Hexa-atomic mixing solutions is poured in the separating funnel, then added oil phase methylene chloride 20ml, then place on the vibration ware, vibration mixes 10min, becomes: water+oil phase mixed solution, leave standstill 5min, and water and separation of oil are collected oil phase liquid;
The deionized water wash oil phase liquid
Oil phase liquid is placed separating funnel, add deionized water 100ml, shake the vibration separating funnel, oil phase liquid is fully mixed with water, become: water+oil phase mixed solution, leave standstill 5min, water and separation of oil are collected oil phase liquid;
The oil phase liquid washing repeats 3 times;
Vacuum is revolved steaming, removes organic solvent
Oil phase liquid is added in the single port flask, then place vacuum to revolve on the steaming machine and revolve steaming, revolve and steam 40 ℃ of temperature, vacuum tightness 0.08Pa revolves steaming time 30min;
Naturally cool at random 25 ℃ after revolving steaming;
Revolve and steam rear one-tenth: yellow oil product
Column chromatography is purified
The dress post: the 300g dry silica gel is placed beaker, add sherwood oil 300ml, stir with glass stick, become mixed solution, then add in the chromatography column, top adds absorbent cotton 0.5g;
Drip washing: yellow oil product is added in the chromatography column, carry out drip washing with sherwood oil 300ml;
Collect: the yellow petroleum ether solution after the drip washing;
Yellow petroleum ether solution is transferred in the single necked round bottom flask, then places vacuum to revolve on the steaming machine and revolve steaming, remove sherwood oil, revolve the steaming temperature 50 C, vacuum tightness 0.08Pa revolves steaming time 60min;
Get after revolving steaming: yellow-white oily product
Recrystallization is purified
Recrystallization is purified and is carried out in the single port Florence flask, yellow-white oily product is placed the single port Florence flask, the single port Florence flask is placed on the electric heating agitator, add ethanol 15ml, access water cycle prolong, 90 ℃ ± 2 ℃ of Heating temperatures, 120min is stirred in vibration, then while hot solution is placed on the chrysanthemum shape filter paper on the filter flask and filters, the filtering insolubles, collect solution, after the solution cooling, separate out white needle-like crystals;
White needle-like crystals is: nitrogen-(6-bromine hexyl) carbazole
(2) synthetic 5-bromo-oxine sodium
1. prepare aqueous sodium hydroxide solution
Sodium hydroxide 2g ± 0.001g is placed beaker, add deionized water 10ml ± 0.001ml, stir 5min, become: the aqueous sodium hydroxide solution of 5mol/L;
2. synthesize in four-hole boiling flask and carry out, four-hole boiling flask is placed on the electric heating agitator, on four-hole boiling flask, insert successively from left to right thermometer, dropping funnel, agitator, water cycle prolong;
3. take by weighing: 5-bromo-oxine 8.96g ± 0.001g
Measure: ethanol 60ml ± 1ml
Add in the four-hole boiling flask;
4. open the electric heating agitator, the water cycle prolong, temperature rises to 70 ℃ ± 2 ℃;
5. aqueous sodium hydroxide solution is added dropping funnel and dropping, rate of addition 1.2ml/min, the limit vibration is stirred, limit water cycle condensation, time 60min, yellowly mixing solutions in the four-hole boiling flask, that is: yellow 5-bromo-oxine+ethanol+sodium hydroxide+deionized water quaternary mixing solutions;
Reaction formula is:
Building-up reactions is closed electric heating agitator, water cycle prolong after finishing, and makes it naturally cool to 25 ℃ with bottle;
6. suction filtration
Yellow quaternary mixing solutions is placed Büchner funnel on the filter flask, carry out suction filtration with two layers of fast qualitative filter paper, retain the product filter cake on the filter paper, waste liquid is evacuated in the filter flask;
7. vacuum-drying
The product filter cake is placed on the quartz container, then place vacuum drying oven to carry out drying, 40 ℃ ± 2 ℃ of drying temperatures, vacuum tightness 0.09Pa, time of drying, 1440min got after the drying: buff powder, that is: 5-bromo-oxine sodium;
(3) synthetic 5-bromo-8-benzyloxy quinoline
1. prepare chloro benzyl+nitrogen, nitrogen-dimethyl formamide mixing solutions
Chloro benzyl 5.8ml ± 0.001ml is placed beaker, add nitrogen, nitrogen-dimethyl formamide 15ml ± 1ml stirs 5min, becomes: chloro benzyl+nitrogen, nitrogen-dimethyl formamide Binary Mixtures;
2. synthesize and in four-hole boiling flask, carry out, four-hole boiling flask is placed on the electric heating agitator, on four-hole boiling flask, insert successively from left to right nitrogen tube, dropping funnel, extraction pipe, water cycle prolong;
3. open the extraction pipe 5min that bleeds, then logical nitrogen 5min substitutes gas and repeats 3 times;
4. take by weighing: 5-bromo-oxine sodium 9.84g ± 0.001g
Measure: nitrogen, nitrogen-dimethyl formamide 40ml ± 1ml
Add in the four-hole boiling flask;
5. open the electric heating agitator, be heated to 90 ℃ ± 2 ℃, stir, open water circulating condensing pipe carries out the water cycle condensation;
6. with chloro benzyl+nitrogen, nitrogen-dimethyl formamide Binary Mixtures adds in the dropping funnel, and drips rate of addition 1.2ml/min;
Stir on limit heating, limit, the limit drips, limit water cycle condensation, and time 240min becomes reaction soln, that is: chloro benzyl+nitrogen, nitrogen-dimethyl formamide+5-bromo-oxine sodium ternary mixing solutions;
Reaction formula is as follows
7. prepare frozen water
Deionized water 200ml is placed beaker, then place refrigerator, make deionized water be down to 0 ℃ ± 1 ℃ by 25 ℃, become frozen water;
8. the ternary mixing solutions is added while hot in 0 ℃ the frozen water, stir 20min, have pale solid to separate out in the whipping process, become: the canescence mixture of ice and water;
9. suction filtration
The canescence mixture of ice and water is placed the Büchner funnel on filter flask top, carry out suction filtration with two layers of fast qualitative filter paper, retain the product filter cake on the filter paper, waste liquid is evacuated in the filter flask;
10. deionized water wash, filtration
The product filter cake is placed beaker, adds deionized water 100ml, agitator treating 10min, then at filter flask with two layers of fast qualitative filter paper filtering;
Deionized water wash, filtration repeat three times;
The isopropyl ether washing
The product filter cake is placed beaker, add isopropyl ether 10ml, agitator treating 10min: filter cake+isopropyl ether mixed solution;
Suction filtration
Mixed solution is placed the Büchner funnel of filter flask, carry out suction filtration with two layers of fast qualitative filter paper, retain the product filter cake on the filter paper, waste liquid is evacuated in the filter flask;
Vacuum-drying
The product filter cake is placed quartz container, then places vacuum drying oven dry, vacuum tightness 0.09Pa, 40 ℃ of drying temperatures, time of drying 1440min;
After the drying: white powder, that is: 5-bromo-8-benzyloxy quinoline;
(4) synthetic 5-(4,4,5,5-tetramethyl--1,3,2-oxa-borine-two base)-8-benzyloxy quinoline
1. prepare in four-hole boiling flask and carry out, four-hole boiling flask is placed on the electric heating agitator, extraction pipe, nitrogen tube, dropping funnel, water cycle prolong are set on four-hole boiling flask from left to right;
2. extract air 5min in the four-hole boiling flask, then pass into nitrogen 5min, substitute gas and repeat three times;
3. take by weighing: 5-bromo-8-benzyloxy quinoline 4.713g ± 0.001g
Measure: triethylamine 15ml ± 1ml
Measure: tetrahydrofuran (THF) 75ml ± 1ml
Take by weighing catalyzer: tetrakis triphenylphosphine palladium 0.52g ± 0.0001g
Add in the four-hole boiling flask;
4. open the electric heating agitator, be warming up to 70 ℃ ± 2 ℃;
Open water circulating condensing pipe carries out the water circulation condensation;
Agitator stirs 10min;
5. add 4,4,5,5-tetramethyl--1,3,2-oxa-borine 2.4ml ± 0.001ml by dropping funnel fast;
Continue to stir 1440min;
To carry out chemical reaction, reaction formula is as follows:
6. reaction finishes, and closes electric heating agitator, water cycle prolong, makes it be cooled to 25 ℃ with bottle;
Become after the reaction: 5-bromo-8-benzyloxy quinoline+triethylamine+tetrahydrofuran (THF)+tetrakis triphenylphosphine palladium+4,4,5,5-tetramethyl--1,3, five yuan of mixing solutionss of 2-oxa-borine;
7. dilute, remove by filter catalyzer with ether
Ether 100ml is added in the four-hole boiling flask by dropping funnel, then insert and turn on agitator, stir 10min, become: hexa-atomic dilution mixing solutions;
Hexa-atomic dilution mixing solutions is placed the Büchner funnel of filter flask, with two layers of fast qualitative filter paper suction filtration, retain the catalyzer tetrakis triphenylphosphine palladium on the filter paper, and remove;
Reaction soln is: 5-bromo-8-benzyloxy quinoline+triethylamine+tetrahydrofuran (THF)+4,4,5,5-tetramethyl--1,3,2-oxa-borine+ether five elementary reaction solution;
8. vacuum is revolved steaming, removes organic solvent
Five elementary reaction solution are placed the single port flask, then place vacuum to revolve on the steaming machine and revolve steaming, remove organic solvent, vacuum tightness 0.08Pa revolves and steams 40 ℃ of temperature, revolves steaming time 30min;
Get after revolving steaming: yellow oil product;
9. column chromatography is purified
The dress post: the 300g dry silica gel is placed beaker, add ether 300ml, stir into mixing solutions with agitator, then add in the chromatography column, top adds absorbent cotton 0.5g;
Drip washing: yellow oil product is added in the chromatography column, carry out drip washing with ether 500ml;
Collect: the yellow diethyl ether solution after the drip washing;
10. vacuum is revolved steaming, removes ether
Yellow diethyl ether solution after the drip washing is placed the single port flask, then place vacuum to revolve on the steaming machine and revolve steaming, vacuum tightness 0.08Pa revolves and steams 40 ℃ of temperature, revolves steaming time 60min;
Get after revolving steaming: the white powder product
That is: 5-(4,4,5,5-tetramethyl--1,3,2-oxa-borine-two base)-8-benzyloxy quinoline
(5) synthetic nitrogen-[6-(8-benzyloxy quinolyl)-hexyl] carbazole
1. synthesize in four-hole boiling flask and carry out, four-hole boiling flask is placed on the electric mantle, electric mantle is placed on the electric heating agitator, on four-hole boiling flask, insert successively from left to right extraction pipe, nitrogen tube, dropping funnel, water cycle prolong;
2. prepare aqueous sodium carbonate
With yellow soda ash 5.088g ± 0.001g, deionized water 24ml ± 0.01ml, place beaker, stir, become: aqueous sodium carbonate, concentration are 2mol/L;
3. open extraction pipe, extract air 5min in the bottle, then be filled with nitrogen 5min, substitute gas and repeat three times;
4. take by weighing: 5-(4,4,5,5-tetramethyl--1,3,2-oxa-borine-two base)-8-benzyloxy quinoline 1.588g ± 0.001g
Take by weighing: nitrogen-(6-bromine hexyl) carbazole 1.32g ± 0.001g
Take by weighing: tetrakis triphenylphosphine palladium 0.0693g ± 0.0001g
Measure: ethanol 4ml ± 0.001ml
Measure: benzene 20ml ± 1ml
Add in the four-hole boiling flask;
5. open the electric heating agitator, stir ware, open water circulating condensing pipe, temperature rises to 90 ℃ ± 2 ℃, stirs 10min;
6. aqueous sodium carbonate 24ml is added in the dropping funnel, in bottle, drip rate of addition 1ml/min;
The limit drips, stir on the limit, heat on the limit, limit water cycle condensing reflux, time 1440min;
To carry out chemical reaction, reaction formula is as follows:
7. after reaction finishes, close the electric heating agitator, stir ware, water cycle prolong, make it be cooled to 25 ℃ with bottle, become in the four-hole boiling flask: 5-(4,4,5,5-tetramethyl--1,3,2-oxa-borine-two base)-8-benzyloxy quinoline+nitrogen-(6-bromine hexyl) hexa-atomic mixing solutions of carbazole+tetrakis triphenylphosphine palladium+ethanol+yellow soda ash+deionized water;
8. benzene extracts secondary
Hexa-atomic mixing solutions is placed separating funnel, add benzene 20ml, vibration mixes 5min, leaves standstill, and water is lower, and oil phase is removed aqueous phase solution upper, retains oil phase liquid, and collects;
The benzene extraction repeats secondary;
9. deionized water wash, separating funnel separates
Oil phase liquid is placed separating funnel, add deionized water 100ml, vibration mixes 5min, makes water, separation of oil, and water is lower, and oil phase is removed water upper, retains oil phase;
10. vacuum is revolved steaming, removes organic solvent
Oil-phase solution is placed the single port flask, place vacuum to revolve steaming machine inward turning and steam, vacuum tightness 0.08Pa revolves and steams 40 ℃ of temperature, revolves steaming time 30min;
Get after revolving steaming: the yellow oily crude product
Column chromatography is purified
The dress post: the 300g dry silica gel is placed beaker, add sherwood oil 300ml, stir into mixing solutions with glass stick, then add in the chromatography column, top adds absorbent cotton 0.5g;
Drip washing: yellow oil product is added in the chromatography column, carry out drip washing with sherwood oil 500ml;
Collect: the yellow petroleum ether solution after the drip washing;
After the purification: oil phase crude product+sherwood oil mixed solution;
Vacuum is revolved to steam and is removed sherwood oil
Mixed solution is placed beaker, then place vacuum to revolve on the steaming machine and revolve steaming, revolve the steaming temperature 50 C, vacuum tightness 0.08Pa revolves steaming time 60min, revolve after the steaming: yellow oil product;
Vacuum-drying
The yellow oil product that to revolve after the steaming places loft drier, and vacuum tightness is 0.09Pa, 40 ℃ of drying temperatures, time of drying 1440min;
It is end product after dry: yellow oil product
That is: nitrogen-[6-(8-benzyloxy quinolyl)-hexyl] carbazole
That is: C
ZThe BQ yellow oil product
(6) detect, analyze, characterize
Synthetic yellow oil product is detected analysis and sign;
To C
ZThe molecular configuration of BQ yellow oil product is analyzed;
To C
ZThe frontier molecular orbitals of BQ is analyzed;
To C
ZThe ultraviolet-visible spectrum of BQ is analyzed;
To C
ZThe fluorescence spectrum of BQ is analyzed;
To C
ZThe photoluminescence spectra of BQ is analyzed;
Conclusion: Nitrogen in Products-[6-(8-benzyloxy quinolyl)-hexyl] carbazole is yellow oily;
Nitrogen in Products-[6-(8-benzyloxy quinolyl)-hexyl] carbazole is electroluminescent organic material, blue light-emitting;
(7) product stores
Synthetic yellow oil product is placed brown transparent Glass Containers, and airtight lucifuge stores, and moistureproof, sun-proof, anti-acid-alkali salt corrosion, 20 ℃ ± 2 ℃ of storing temps, relative humidity≤10%.
2. the synthetic method of a kind of nitrogen according to claim 1-[6-(8-benzyloxy quinolyl)-hexyl] carbazole is characterized in that: described C
ZThe preparation of BQ end product is carried out at four-hole boiling flask, control panel at electric heating agitator (1) is provided with pilot lamp (2), trip switch (3), stirring ware (4), thermometer (5), be electric mantle (21) on the top of electric heating agitator (1), be four-hole boiling flask (6) at electric mantle (21), be provided with successively from left to right extraction pipe (16), nitrogen tube (13), dropping funnel (11) and control valve (12), water cycle prolong (7) and air outlet (8), water-in (9), water outlet (10) on four-hole boiling flask (6) top; It is hexa-atomic mixing solutions (19) in four-hole boiling flask; Be aqueous sodium carbonate (20) in dropping funnel (11); Extraction pipe (16) connects off-gas pump (18), and by extraction valve (17) control, nitrogen tube (13) connects nitrogengas cylinder (15), and is controlled by nitrogen valve (14).
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