CN103509019B - Cool compounds of a kind of dibenzo and preparation method thereof - Google Patents
Cool compounds of a kind of dibenzo and preparation method thereof Download PDFInfo
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- CN103509019B CN103509019B CN201210204274.3A CN201210204274A CN103509019B CN 103509019 B CN103509019 B CN 103509019B CN 201210204274 A CN201210204274 A CN 201210204274A CN 103509019 B CN103509019 B CN 103509019B
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- Prior art keywords
- cool
- bis
- compounds
- alkyl
- dibenzo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- KJOLVZJFMDVPGB-UHFFFAOYSA-N perylenediimide Chemical class C=12C3=CC=C(C(NC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)NC(=O)C4=CC=C3C1=C42 KJOLVZJFMDVPGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004327 boric acid Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 19
- 150000003949 imides Chemical class 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- 238000003808 methanol extraction Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229960001866 silicon dioxide Drugs 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- -1 perylene acid anhydride Chemical class 0.000 abstract description 186
- 230000005669 field effect Effects 0.000 abstract description 13
- 125000003118 aryl group Chemical group 0.000 abstract description 10
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 abstract description 9
- 125000003545 alkoxy group Chemical group 0.000 abstract description 5
- 125000001246 bromo group Chemical class Br* 0.000 abstract description 5
- 238000010189 synthetic method Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 150000001412 amines Chemical class 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000007363 ring formation reaction Methods 0.000 abstract description 2
- 238000001819 mass spectrum Methods 0.000 description 15
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- HPUOAJPGWQQRNT-UHFFFAOYSA-N pentoxybenzene Chemical compound CCCCCOC1=CC=CC=C1 HPUOAJPGWQQRNT-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 8
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 239000004973 liquid crystal related substance Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 7
- 235000010338 boric acid Nutrition 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 0 *C(C=C1C(C=C(C(C(C=C2c3c4)C(N5*)=O)C6=C2C(C2=C(C(C7)C(N8*)O)C(C9)C8=O)=C7c3cc(O)c4O*)C5=O)=C6C2=C9C1C1)=C1O Chemical compound *C(C=C1C(C=C(C(C(C=C2c3c4)C(N5*)=O)C6=C2C(C2=C(C(C7)C(N8*)O)C(C9)C8=O)=C7c3cc(O)c4O*)C5=O)=C6C2=C9C1C1)=C1O 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 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 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006219 1-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- YADWNLPLTAKWJQ-UHFFFAOYSA-N CC(CP)CCCCCCCCCCCC Chemical compound CC(CP)CCCCCCCCCCCC YADWNLPLTAKWJQ-UHFFFAOYSA-N 0.000 description 1
- WLBQUWMLQXAKAG-UHFFFAOYSA-N CCCCCCCCC(CCCCCC)CN(C(c1ccc(C2C(CC3C(N4CC(CCCCCC)CCCCCCCC)=O)C(CC5OCCCCC)=CC=C5OCCCCC)c5c1c1ccc5-c(c(C(CCC5OCCCCC)C=C5OCCCCC)c5)c2c3c5C4=O)O)C1=O Chemical compound CCCCCCCCC(CCCCCC)CN(C(c1ccc(C2C(CC3C(N4CC(CCCCCC)CCCCCCCC)=O)C(CC5OCCCCC)=CC=C5OCCCCC)c5c1c1ccc5-c(c(C(CCC5OCCCCC)C=C5OCCCCC)c5)c2c3c5C4=O)O)C1=O WLBQUWMLQXAKAG-UHFFFAOYSA-N 0.000 description 1
- 239000004985 Discotic Liquid Crystal Substance Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003542 behavioural effect Effects 0.000 description 1
- ZIQCCIAIROIHHR-UHFFFAOYSA-N benzene;boric acid Chemical class OB(O)O.C1=CC=CC=C1 ZIQCCIAIROIHHR-UHFFFAOYSA-N 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 229940049706 benzodiazepine Drugs 0.000 description 1
- 125000005619 boric acid group Chemical class 0.000 description 1
- VPUGDVKSAQVFFS-UHFFFAOYSA-N c(c(cc1)c2c3c1cc1)cc(cc4)c2c2c4ccc4c2c3c1cc4 Chemical compound c(c(cc1)c2c3c1cc1)cc(cc4)c2c2c4ccc4c2c3c1cc4 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000009304 pastoral farming Methods 0.000 description 1
- UWBZUWHVXOFZFZ-UHFFFAOYSA-N pentadecan-2-ylphosphane Chemical compound CC(CCCCCCCCCCCCC)P UWBZUWHVXOFZFZ-UHFFFAOYSA-N 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001907 polarising light microscopy Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000008521 reorganization Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-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
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
- C09K19/3483—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a non-aromatic ring
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/731—Liquid crystalline materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention relates to cool compounds of a kind of dibenzo and preparation method thereof, the structure of the compounds of this invention is as shown in general formula (I):
r and R in its Chinese style
1identical or different alkyl respectively.The present invention uses two easily obtained bromines for perylene acid anhydride or mixture, and in organic solvent with the sub-amide compound of amine reaction preparation two bromo, this compound and 3, the phenylo boric acid of 4 alkoxyl group replacements is at Pd(PPh
3)
4carry out suzuki coupled reaction under katalysis and prepare the perylene diimide compounds that aryl replaces, this product under DDQ effect further by oxidizing reaction and ring formation has the cool compounds of transferring charge class.Synthetic method of the present invention is simple, and yield is high, can be widely used in Organic Light Emitting Diode, field effect transistor and solar cell.
Description
Technical field
The present invention relates to cool compounds of a kind of dibenzo and preparation method thereof, structure is the preparation method that this kind of charge transport compound of the cool compounds of sub-amide group is contained in molecule both sides specifically, and the molecular structure of this compound is as follows:
Background technology
Organic charge transport material has the advantages such as material source is abundant, cost is low, toxicity is little, be easy to machine-shaping and carry out chemically modified, can make big area Grazing condition thin-film device, waste treatment is easy, becomes the mainstay material system of the photoelectric devices such as optical conductor today (as duplicating machine, laser printer, digital printer etc.), solar cell, field effect transistor and electroluminescent.
The compounds that discotic mesogenic is made up of discshaped rigidizing stone and periphery flexible side-chains, because columnar superstructures can be formed by pi-pi accumulation, thus be that electric charge provides condition along axis of a cylinder transmission, therefore in organic electronic devices structure, there is very good application prospect.
Cool class disc liquid-crystal compounds receives in recent years and studies comparatively widely.It is supplied to system one and at least has 7 and large conjugation fragrance rigidity disc-shaped core together, and make formed columnar structure overlapping area larger, Reorganization Energy obviously reduces, and advantageously transmits vertically in electric charge.The basic structure of cool compounds is as follows:
The cool derivative of its dibenzo has having structure:
It is incorporated with again two phenyl ring in upper and lower position on cool architecture basics, the compounds be made up of discshaped rigidizing stone and periphery flexible side-chains, because columnar superstructures can be formed by pi-pi accumulation, thus be that electric charge provides condition along axis of a cylinder transmission, therefore in organic electronic devices structure, there is very good application prospect.
Perylene diimides molecule has the molecular configuration of plane, very strong π-π interacts, the almost fluorescence quantum yield of 100% and good photo and thermal stability, and these character determine the ideal building blocks as structure organic photoelectrical material.The application of perylene diimides class discotic mesogenic in electron device is also very extensive:
As semiconductor material, the application of discotic mesogenic in organic electronic devices obtains paying close attention to very widely, and it can be used as the active component of Organic Light Emitting Diode (OLED), field effect transistor (FET) and solar cell.Perylene diimides class liquid crystal molecule has larger aromatic series rigid nuclear compared with other liquid crystal unit, and very strong π-π interacts, and can form more large-area mutual superposition between adjacent aromatic nucleus, there is higher carrier mobility, be conducive to its application in the devices.
1, Organic Light Emitting Diode
The conjugation large π key of discotic mesogenic material makes it have electroluminescent characteristic, there is using value in organic field-effect tube field.Such as, triphenylene liquid crystals primitive is exactly good hole mobile material.And new discotic liquid crystal material perylene diimides and derivative thereof are the n-type semiconductor of excellent property, and very strong π-π interacts, and can form more large-area mutual superposition between adjacent aromatic nucleus, there is higher carrier mobility, be conducive to its application in the devices.As shown in Figure 1, be organic LED structure schematic diagram.
2, organic field-effect tube
Field effect transistor mainly relies on the conductivity of electric field controls semiconductor material, comprises three electrodes: source electrode, drain and gate.Grid voltage controls the electric current between source electrode and drain path, so field effect transistor is voltage controlled element.Perylene diimides and derivative thereof, as the n-type semiconductor of excellent property, have very high stability in atmosphere, and can height of formation order thin film, can be used for making field effect transistor, and the structure of organic field-effect tube as shown in Figure 2.
3, photovoltaic device
Photocell or solar cell are devices transform light energy being become electric energy, and its similar is in light emitting diode, and photocell structure as shown in Figure 3.With light emitting diode unlike the photronic semiconductor layer that enlivens by inorganic silicon or form after photon is injected into semi-conductor to the mixture of body and acceptor, inspire electron-hole pair, this electron-hole pair is separated at p-n junction place, collecting via electrode respectively outputs to outside cell body, forms electric current.Condensed-nuclei aromatics demonstrates excellent performance in this device application.Li Ru the photocell of ， perylene diimides and the cool formation of six benzos at 490nm wavelength time, quantum yield is up to 34%.
Therefore with the sub-acid amides of perylene two, for primitive constructs, organic Optoelectronic molecular materials has very good application prospect by organic electronic devices structure.
The present invention is studied containing the cool derivative of sub-amides dibenzo, and this compounds and synthetic method thereof are not reported at present.
Summary of the invention
The object of the present invention is to provide a kind of containing the cool compound of sub-amides dibenzo and high-level efficiency synthesis and preparative method thereof.Of the present invention containing the cool compound of sub-amides dibenzo, be expected to can have self-assembly performance as outstanding, the charge transfer material of long-range order, fast transport electric charge can be realized, become the main raw composition of the photoelectric devices such as optical conductor (as duplicating machine, laser printer, digital printer etc.), solar cell, field effect transistor and electroluminescent.
The cool compounds of a kind of dibenzo, for containing the cool compound of sub-amides dibenzo, its structure is as shown in general formula (I):
R and R in its Chinese style
1identical or different alkyl respectively.
Described alkyl can preferred C
1-C
18linear primary alkyl or branched primary alkyl.
Described C
1-C
18linear primary alkyl, meet general formula C
nh
2n+1wherein n be less than or equal to 18 integer, i.e. n≤18, as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl.
Described C
1-C
18branched primary alkyl preferred:
(1) 2-CH
3r
11, R
11for C
3-C
18straight chained alkyl, as 2-methyl-propyl, 2-methyl butyl, 2-methyl amyl, 2-methylhexyl, 2-methylheptyl, 2-Methyl Octyl, 2-Nonyl, 2-methyldecyl, 2-methylundecyl, 2-methyl dodecyl, 2-methyltridec base, 2-methyltetradecylphosphine base, 2-methyl pentadecyl, 2-methyl hexadecyl, 2-methyl heptadecyl, 2-methyl octadecyl;
(2) 2-C
2h
5r
12, R
12for C
4-C
18straight chained alkyl, as 2-ethyl-butyl, 2-ethyl pentyl group, 2-ethylhexyl, 2-ethylheptyl, 2-ethyloctanyl, 2-ethylnonanyl, 2-ethyl decyl, 2-ethyl undecyl, 2-ethyl dodecyl, 2-ethyl tridecyl, 2-ethyl tetradecyl, 2-ethyl pentadecyl, 2-ethylhexadecyl, 2-ethyl heptadecyl, 2-ethyl octadecyl;
(3) 2-C
3h
7r
13, R
13for C
5-C
18straight chained alkyl, as 2-propylpentyl, 2-propyl group hexyl, 2-propylheptyl, 2-propyl octyl, 2-propyl group nonyl, 2-propyl group decyl, 2-propyl group undecyl, 2-propyl group dodecyl, 2-propyl group tridecyl, 2-propyl group tetradecyl, 2-propyl group pentadecyl, 2-propyl group hexadecyl, 2-propyl group heptadecyl, 2-propyl group octadecyl;
(4) 2-C
4h
9r
14, R
14for C
6-C
18straight chained alkyl, as 2-butyl hexyl, 2-butyl heptyl, 2-butyl octyl, 2-butyl nonyl, 2-butyl decyl, 2-butyl undecyl, 2-butyl dodecyl, 2-butyl tridecyl, 2-butyl tetradecyl, 2-butyl pentadecyl, 2-butyl hexadecyl, 2-butyl heptadecyl, 2-butyl octadecyl;
(5) 2-C
5h
11r
15, R
15for C
7-C
18straight chained alkyl, as 2-amyl group heptyl, 2-amyl group octyl group, 2-pentylnonanyi, 2-amyl group decyl, 2-amyl group undecyl, 2-amyl group dodecyl, 2-amyl group tridecyl, 2-amyl group tetradecyl, 2-amyl group pentadecyl, 2-amyl group hexadecyl, 2-amyl group heptadecyl, 2-amyl group octadecyl;
(6) 2-C
6h
13r
16, R
16for C
8-C
18straight chained alkyl, as 2-hexyl octyl group, 2-hexyl nonyl, 2-hexyl decyl, 2-hexyl undecyl, 2-hexyl dodecyl, 2-hexyl tridecyl, 2-hexyl tetradecyl, 2-hexyl pentadecyl, 2-hexyl hexadecyl, 2-hexyl heptadecyl, 2-hexyl octadecyl;
(7) 2-C
7h
15r
17, R
17for C
9-C
18straight chained alkyl, as 2-heptyl nonyl, 2-heptyl decyl, 2-heptylundecanoic base, 2-heptyl dodecyl, 2-heptyl tridecyl, 2-heptyl tetradecyl, 2-heptyl pentadecyl, 2-heptyl hexadecyl, 2-heptyl heptadecyl, 2-heptyl octadecyl;
(8) 2-C
8h
17r
18, R
18for C
10-C
18straight chained alkyl, as 2-octyl-decyl, 2-octyl group undecyl, 2-octyldodecyl, 2-octyl group tridecyl, 2-octyl group tetradecyl, 2-octyl group pentadecyl, 2-octyl group hexadecyl, 2-octyl group heptadecyl, 2-octyl group octadecyl;
(9) 2-C
9h
19r
19, R
19for C
11-C
18straight chained alkyl, as 2-nonyl undecyl, 2-nonyl dodecyl, 2-nonyl tridecyl, 2-nonyl tetradecyl, 2-nonyl pentadecyl, 2-nonyl hexadecyl, 2-nonyl heptadecyl, 2-nonyl octadecyl,
(10) 2-C
10h
21r
20, R
20for C
12-C
18straight chained alkyl, as 2-decyl dodecyl, 2-decyl tridecyl, 2-decyl tetradecyl, 2-decyl pentadecyl, 2-decyl hexadecyl, 2-decyl heptadecyl, 2-decyl octadecyl;
(11) 1-CH
3r
21, R
21for C
2-C
18straight chained alkyl, as 1-methylethyl, 1-methyl-propyl, 1-methyl butyl, 1-methyl amyl, 1-methylhexyl, 1-methylheptyl, 1-Methyl Octyl, 1-Nonyl, 1-methyldecyl, 1-methylundecyl, 1-methyl dodecyl, 1-methyltridec base, 1-methyltetradecylphosphine base, 1-methyl pentadecyl, 1-methyl hexadecyl, 1-methyl heptadecyl, 1-methyl octadecyl;
(12) 1-C
2h
5r
11, R
11for C
3-C
18straight chained alkyl, as 1-ethyl propyl, 1-ethyl-butyl, 1-ethyl pentyl group, 1-ethylhexyl, 1-ethylheptyl, 1-ethyloctanyl, 1-ethylnonanyl, 1-ethyl decyl, 1-ethyl undecyl, 1-ethyl dodecyl, 1-ethyl tridecyl, 1-ethyl tetradecyl, 1-ethyl pentadecyl, 1-ethylhexadecyl, 1-ethyl heptadecyl, 1-ethyl octadecyl;
(13) 1-C
3h
7r
12, R
12for C
4-C
18straight chained alkyl, as 1-butyl, 1-propylpentyl, 1-propyl group hexyl, 1-propylheptyl, 1-propyl octyl, 1-propyl group nonyl, 1-propyl group decyl, 1-propyl group undecyl, 1-propyl group dodecyl, 1-propyl group tridecyl, 1-propyl group tetradecyl, 1-propyl group pentadecyl, 1-propyl group hexadecyl, 1-propyl group heptadecyl, 1-propyl group octadecyl;
(14) 1-C
4h
9r
13, R
13for C
5-C
18straight chained alkyl, as 1-butyl amyl group, 1-butyl hexyl, 1-butyl heptyl, 1-butyl octyl, 1-butyl nonyl, 1-butyl decyl, 1-butyl undecyl, 1-butyl dodecyl, 1-butyl tridecyl, 1-butyl tetradecyl, 1-butyl pentadecyl, 1-butyl hexadecyl, 1-butyl heptadecyl, 1-butyl octadecyl;
(15) 1-C
5h
11r
14, R
14for C
6-C
18straight chained alkyl, as 1-amyl group hexyl, 1-amyl group heptyl, 1-amyl group octyl group, 1-pentylnonanyi, 1-amyl group decyl, 1-amyl group undecyl, 1-amyl group dodecyl, 1-amyl group tridecyl, 1-amyl group tetradecyl, 1-amyl group pentadecyl, 1-amyl group hexadecyl, 1-amyl group heptadecyl, 1-amyl group octadecyl;
(16) 1-C
6h
13r
15, R
15for C
7-C
18straight chained alkyl, as 1-hexyl heptyl, 1-hexyl octyl group, 1-hexyl nonyl, 1-hexyl decyl, 1-hexyl undecyl, 1-hexyl dodecyl, 1-hexyl tridecyl, 1-hexyl tetradecyl, 1-hexyl pentadecyl, 1-hexyl hexadecyl, 1-hexyl heptadecyl, 1-hexyl octadecyl;
(17) 1-C
7h
15r
16, R
16for C
8-C
18straight chained alkyl, as 1-heptyl octyl group, 1-heptyl nonyl, 1-heptyl decyl, 1-heptylundecanoic base, 1-heptyl dodecyl, 1-heptyl tridecyl, 1-heptyl tetradecyl, 1-heptyl pentadecyl, 1-heptyl hexadecyl, 1-heptyl heptadecyl, 1-heptyl octadecyl;
(18) 1-C
8h
17r
17, R
17for C
9-C
18straight chained alkyl, as 1-octyl group nonyl, 1-octyl-decyl, 1-octyl group undecyl, 1-octyldodecyl, 1-octyl group tridecyl, 1-octyl group tetradecyl, 1-octyl group pentadecyl, 1-octyl group hexadecyl, 1-octyl group heptadecyl, 1-octyl group octadecyl;
(19) 1-C
9h
19r
18, R
18for C
10-C
18straight chained alkyl, as 1-nonyl decyl, 1-nonyl undecyl, 1-nonyl dodecyl, 1-nonyl tridecyl, 1-nonyl tetradecyl, 1-nonyl pentadecyl, 1-nonyl hexadecyl, 1-nonyl heptadecyl, 1-nonyl octadecyl;
(20) 1-C
10h
21r
19, R
19for C
11-C
18straight chained alkyl, as 1-decyl undecyl, 1-decyl dodecyl, 1-decyl tridecyl, 1-decyl tetradecyl, 1-decyl pentadecyl, 1-decyl hexadecyl, 1-decyl heptadecyl, 1-decyl octadecyl.
R is C
1-C
18linear primary alkyl or branched primary alkyl, R1 can be C
1-C
18linear primary alkyl.R and R
1can more preferably C
1-C
6straight chained alkyl.
The cool compounds of dibenzo of the present invention is symmetrical structure.
The preparation method of the cool compounds of dibenzo of the present invention, comprises the steps:
The sub-amide compound of (1) two bromo, its structure as shown in general formula (II), with 3, the phenylo boric acid that 4 alkoxyl groups replace, its structure, as shown in general formula (III), is carried out suzuki coupled reaction and is prepared the perylene diimide compounds that aryl replaces;
(2) aryl of step (1) gained replaces perylene diimide compounds, its structure is as shown in general formula (IV), there is oxidizing reaction further and ring formation has the cool compounds of dibenzo of transferring charge class DDQ (DDQ) effect is lower, its structure is as shown in logical formula V
Wherein, R and R
1identical or different alkyl respectively.
Described alkyl can preferred C
1-C
18linear primary alkyl or branched primary alkyl.
Above-mentioned C
1-C
18linear primary alkyl be C
1-C
18straight chained alkyl, meet general formula C
nh
2n+1, as: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl.
Above-mentioned branched primary alkyl, preferred 2-CH
3r
11, 2-C
2h
5r
12, 2-C
3h
7r
13, 2-C
4h
9r
14, 2-C
5h
11r
15, 2-C
6h
13r
16, 2-C
7h
15r
17, 2-C
8h
17r
18, 2-C
9h
19r
19, 2-C
10h
21r
20, 1-CH
3r
21, 1-C
2h
5r
11, 1-C
3h
7r
12, 1-C
4h
9r
13, 1-C
5h
11r
14, 1-C
6h
13r
15, 1-C
7h
15r
16, 1-C
8h
17r
17, 1-C
9h
19r
18and 1-C
10h
21r
19, wherein R11 is C
3-C
18straight chained alkyl, R
12for C
4-C
18straight chained alkyl, R
13for C
5-C
18straight chained alkyl, R
14for C
6-C
18straight chained alkyl, R
15for C
7-C
18straight chained alkyl, R
16for C
8-C
18straight chained alkyl, R
17for C
9-C
18straight chained alkyl, R
18for C
10-C
18straight chained alkyl, R19 is C
11-C
18straight chained alkyl, R
20for C
12-C
18straight chained alkyl, R
21for C
2-C
18straight chained alkyl.Branched primary alkyl is concrete as mentioned before, but described in being not limited to.
R is C
1-C
18linear primary alkyl or branched primary alkyl, R
1can be C
1-C
18linear primary alkyl.R and R
1can more preferably C
1-C
6straight chained alkyl.
Above-mentioned preparation method can represent by reaction process below:
The sub-amide compound of raw material two bromo used in described preparation method, can be easy to by two bromines for perylene acid anhydride or mixture, prepares in organic solvent with amine reaction.
A preparation method for the cool compound of dibenzo, comprises the steps:
(1) 1,7-bis-(3 ', 4 '-dialkoxy phenyl)-N, N '-bis-(alkyl)-3,4:9,10-perylene diimides
At Na
2cO
3the aqueous solution, toluene and CH
3in OH solution, under N2 environment, the two alkane base perylene diimide of 1,7-dibromo and 3,4-dialkoxy phenylo boric acid are at Pd(PPh
3)
4under catalyst action, reacting by heating, obtains 1,7-bis-(3 ', 4 '-dialkoxy phenyl)-N, N '-bis-(alkyl)-3,4:9,10-perylene diimides.
(2) 1,7-bis-(3,3 ', 4,4 '-dialkoxy benzene) cool-N, N '-two (alkyl) imide
In the solution of methylene dichloride and methylsulfonic acid, 1,7-bis-(3 ', 4 '-dialkoxy phenyl)-N, oxydehydrogenation under the effect of N '-bis-(alkyl)-3,4:9,10-perylene diimides DDQ (DDQ) in ice-water bath, obtain 1,7-bis-(3,3 ', 4,4 '-dialkoxy benzene) and cool-N, N '-two (alkyl) imide.
Described alkyl is C
1-C
18linear primary alkyl or branched primary alkyl, specifically as previously mentioned.
The preparation method of the cool compound of described dibenzo, comprises following concrete steps:
(1) 1,7-bis-(3 ', 4 '-dialkoxy phenyl)-N, N '-bis-(alkyl)-3,4:9,10-perylene diimides
At N
2under environment, by Pd(PPh
3)
4toluene solution add the round-bottomed flask that 1,7-dibromo Shuan Wan Ji perylene diimide is housed, then add 2M Na
2cO
3the CH of solution and 3,4-alkoxy benzene boric acid
3oH solution, stirs 48hrs at 70 DEG C.Be cooled to room temperature, add NH3 water and 2N Na
2cO
3solution termination reaction, CHCl
3extraction, washing, anhydrous Na
2sO
4drying, filters, boils off most of solvent, add methanol extraction, if need to purify further, can use silicagel column (CHCl
2: sherwood oil=10:1) purify, from CHCl
3/ recrystallizing methanol obtains dark blue powder.
(2) 1,7-bis-(3,3 ', 4,4 '-dialkoxy benzene) cool-N, N '-two (alkyl) imide
By 1,7-bis-(3 ', 4 '-dialkoxy phenyl)-N, N '-bis-(alkyl)-3,4:9,10-perylene diimides is dissolved in the there-necked flask filling anhydrous methylene chloride and methylsulfonic acid, mixture is cooled to 0 DEG C, adds DDQ(DDQ three times every five minutes points), react and control progress by TLC, react about 30 minutes, then add ice methyl alcohol cancellation reaction, filtering precipitate, then carry out separating-purifying with shorter chromatogram column, the impurity of removing initial point, obtains red solid by methylene dichloride and recrystallizing methanol.
Thermal behavior and Optical Properties
Mesomorphism containing the cool series compound of sub-amides dibenzo prepared by the present invention is observed by thermogravimetric analyzer (TG), differential scanning calorimeter (DSC) and polarizing microscope (POM) and is determined, the analytical results of three kinds of methods can be supported mutually.
Fig. 4 is series compound 1,7-bis-(3,3 ', 4,4 '-didecyl oxygen base benzene) and cool-N, N '-two (2-hexyl octyl group) imide, 1,7-bis-(3,3 ', 4,4 '-tetracosane oxygen base benzene) and cool-N, N '-two (2-hexyl octyl group) imide and 1,7-bis-(3,3 ', 4,4 '-octacosane oxygen base benzene) and the TG of cool-N, N '-two (2-hexyl octyl group) imide closes figure, because these three kinds of compounds are the difference of alkyloxy side chain, conveniently, we it referred to as PDI-Ph-OC
10, PDI-Ph-OC
14, PDI-Ph-OC
18wherein, curve 1 represents PDI-Ph-OC
10, curve 2 represents PDI-Ph-OC
14, curve 3 represents PDI-Ph-OC
18.Temperature when this series compound starts weightlessness obviously can be seen: PDI-Ph-OC in figure
10be 320 DEG C, PDI-Ph-OC
14be 290 DEG C, PDI-Ph-OC
18it is 240 DEG C.Be heated to 600 DEG C, weightlessness is all more than 50%, and this result shows the increase of this series compound due to alkyloxy side chain length, and alkyloxy side chain more easily ruptures, and stable at high temperature is poor.
By analyzing TG test result, in the test of DSC and POM, intensification final temperature is all less than it and starts weightless temperature accordingly, to ensure the stability of sample, Fig. 5 is the DSC graphic representation of this series compound, and temperature rise rate 10K/min, wherein curve 1 represents PDI-Ph-OC
10, curve 2 represents PDI-Ph-OC
14, curve 3 represents PDI-Ph-OC
18.Below 300 DEG C, there is larger endotherm(ic)peak at 60-80 DEG C in three compounds, phase in version occurs, and continuing to heat up does not occur significantly inhaling exothermic peak.
According to DSC test result, three compounds are placed in respectively phase transformation during its intensification of polarized light microscopy Microscopic observation, be equally below 300 DEG C, temperature rise rate is 10 DEG C/min.Fig. 6-a, Fig. 6-b, Fig. 6-c are the compound PDI-Ph-OC observed respectively
10, PDI-Ph-OC
14, PDI-Ph-OC
18pOM figure.
From POM figure, after each compound generation phase in version, observe obviously birefringent phenomenon, illustrate that compound crystal form there occurs change.In observation process, intuitively can see that compound becomes thickness from solid-state, if apply certain external force, then the region with birefringent phenomenon increases.
The present invention has the following advantages:
1, easily preparation fast, and raw material can be bought by business, cheap and easy to get.
2, can be reacted by it and 3,4-different dialkoxy benzene boric acid compounds, prepare the cool compounds of dibenzo of different alkoxy substituent, make obtained compounds property be easy to regulate.
The cool compounds solubleness of 3, being synthesized by this patented method is good, is convenient to the performance test further as transferring charge and disc liquid-crystal compounds.
And of the present invention have larger aromatic series rigid nuclear containing the cool compound of sub-amides dibenzo, can form more large-area mutual superposition, have higher carrier mobility between adjacent aromatic nucleus.Therefore can be used as electric transmission compound is widely used in electron device, as semiconductor material, can be used as the active component of Organic Light Emitting Diode (OLED), field effect transistor (FET) and solar cell.
The invention provides the synthetic method containing the cool series compound of sub-amides dibenzo and this compounds, achieve the preparation of this compounds first; Synthetic method of the present invention is simple, and yield is high.
Below by the drawings and specific embodiments, the present invention will be further described, but and do not mean that limiting the scope of the invention.
Accompanying drawing explanation
Fig. 1 is organic light emitting diode structural representation.
Fig. 2 is organic field-effect tube structure iron.
Fig. 3 is photocell structure figure.
Fig. 4 is series compound PDI-Ph-OC
10, PDI-Ph-OC
14, PDI-Ph-OC
18thermogravimetic analysis (TGA) (TG) close figure.
Fig. 5 is series compound PDI-Ph-OC
10, PDI-Ph-OC
14, PDI-Ph-OC
18dSC close figure.
Fig. 6-a, Fig. 6-b, Fig. 6-c are respectively series compound PDI-Ph-OC
10, PDI-Ph-OC
14, PDI-Ph-OC
18polarizing microscope (POM) under texture pattern.Fig. 6-a:161.1 DEG C, Fig. 6-b:185.8 DEG C, Fig. 6-c:212 DEG C.
Fig. 7 be 1,7-bis-(3 ', 4 '-two pentyloxy phenyl)-N, N '-bis-(dodecyl)-3,4:9,10-perylene diimides proton nmr spectra hydrogen spectrum (
1hNMR) figure.
Fig. 8 be 1,7-bis-(3,3 ', 4,4 '-two amyl phenyl ether) and the proton nmr spectra hydrogen of cool-N, N '-two (hexadecyl) imide spectrum (
1hNMR) figure.
Fig. 9 is 1,7-bis-(3,3 ', 4,4 '-two amyl phenyl ether) and the carbon-13 nmr spectra of cool-N, N '-two (hexadecyl) imide (
13cNMR) figure.
Figure 10 is 1,7-bis-(3,3 ', 4,4 '-two amyl phenyl ether) and mass spectrum (MS) figure of cool-N, N '-two (hexadecyl) imide.
Figure 11 be 1,7-bis-(3 ', 4 '-two pentyloxy phenyl)-N, N ' one or two (2-hexyl octyl group)-3,4:9,10-perylene diimides proton nmr spectra hydrogen spectrum (
1hNMR) figure.
Figure 12 be 1,7-bis-(3,3 ', 4,4 '-two amyl phenyl ether) and the proton nmr spectra hydrogen of cool-N, N '-two (2-hexyl octyl group) imide spectrum (
1hNMR) figure.
Figure 13 is 1,7-bis-(3,3 ', 4,4 '-two amyl phenyl ether) and the carbon-13 nmr spectra of cool-N, N '-two (2-hexyl octyl group) imide (
13cNMR) figure.
Figure 14 is 1,7-bis-(3,3 ', 4,4 '-two amyl phenyl ether) and mass spectrum (MS) figure of cool-N, N '-two (2-hexyl octyl group) imide.
Figure 15 be 1,7-bis-(3 ', 4 '-two pentyloxy phenyl)-N, N ' one or two (1-butyl undecyl)-3,4:9,10-perylene diimides proton nmr spectra hydrogen spectrum (
1hNMR) figure.
Figure 16 be 1,7 two (3,3 ', 4,4 '-two amyl phenyl ether) and the proton nmr spectra hydrogen of cool-N, N '-two (1-butyl undecyl) imide spectrum (
1hNMR) figure.
Figure 17 is 1,7 two (3,3 ', 4,4 '-two amyl phenyl ether) and the carbon-13 nmr spectra of cool-N, N '-two (1-butyl undecyl) imide (
13cNMR) figure.
Figure 18 be 1,7 two (3,3 ', 4,4 '-two amyl phenyl ether) and cool-N, N '-two (1-butyl undecyl) imide mass spectrum (MS) figure.
Embodiment
Embodiment 1
1,1,7-bis-(3 ', 4 '-two pentyloxy phenyl)-N, N '-bis-(dodecyl)-3,4:9,10-perylene diimides---compound (A)
At N
2under environment, by 1.2g(1mmol) Pd(PPh
3)
4toluene (160ml) solution add 8.8g(10mmol is housed) round-bottomed flask of the two Shi bis-Wan Ji perylene diimide of 1,7-dibromo, then add 2M Na
2cO
3the CH of solution (40ml) and 6.4g(22mmol) 3,4-bis-pentyloxy phenylo boric acids
3oH(60ml) solution, stirs 48hrs at 70 DEG C.Be cooled to room temperature, add 5ml NH
3water and 2N Na
2cO
3solution (15ml) termination reaction, CHCl
3extraction, washing, anhydrous Na
2sO
4drying, filters, boils off most of solvent, add methanol extraction, if need to purify further, can use silicagel column (CHCl
2: sherwood oil=10:1) purify, from CHCl
3/ recrystallizing methanol obtains dark blue powder 8.0g, and to be 80%, Mp. be productive rate: 120.1-125.7 DEG C;
By hydrogen nuclear magnetic resonance spectrum analysis, concrete data are:
1hNMR (CDCl
3) δ: 0.978(t, 6H, CH
3), 0.996(t, 6H, CH
3), 1.252(t, 6H, CH
3), 1.35-1.542(m, 52H, CH
2), 1.55(m, 4H, CH
2), 1.79(m, 4H, CH
2), 1.92(m, 4H, CH
2), 3.99 (m, 4H, NCH
2), 4.09 (t, 4H, OCH
2), 4.19(t, 4H, OCH
2), 6.94(s, 2H, ArH), 7.02(m, 4H, ArH), 7.79(d, 2H, PerH) and, 8.14(d, 2H, PerH), 8.489(s, 2H, PerH).Its proton nmr spectra (
1hNMR) as shown in Figure 7.
2,1,7-bis-(3,3 ', 4,4 '-two amyl phenyl ether) cool-N, N '-two (hexadecyl) imide---compound (B)
By 1.33 gram 1, 7-bis-(3 ', 4 '-two pentyloxy phenyl)-N, N '-bis-(hexadecyl)-3, 4:9, 10-perylene diimides (1mmol) is dissolved in the there-necked flask filling 90 milliliters of anhydrous methylene chlorides and 10ml methylsulfonic acid, mixture is cooled to 0 degree, the DDQ(DDQ of 0.7g is added for three times) every five minutes points, reaction controls progress by TLC, react about 30 minutes, then 100ml ice methyl alcohol cancellation reaction is added, filtering precipitate, separating-purifying is carried out again with shorter chromatogram column, the impurity of removing initial point, 0.66g red solid is obtained by methylene dichloride and recrystallizing methanol, productive rate 90%, Mp.>400 DEG C.
By proton nmr spectra, carbon-13 nmr spectra and mass spectroscopy, the product finally obtained, concrete data are
1hNMR (CDCl3) δ: 0.93(t, 6H, CH
3), 1.10(t, 6H, CH
3), 1.17(t, 6H, CH
3), 1.32-1.58(m, 74H, CH
2), 1.79(m, 6H, CH
2), 2.09(m, 4H, CH
2), 3.88 (m, 4H, NCH
2), 4.21(m, 8H, OCH
2), 7.22-8.32(m, 8H, ArH, PerH).
13CNMR(75MHz，CDCl
3)δ：161.59,149.11,122.09,120.67,116.79,116.26,102.57,68.00,39.68,38.12,31.96,31.21,30.22,29.99,29.84,29.78,29.73,29.40,29.12,28.58,27.76,27.20,22.82,22.71,14.10.MS(MALDI-TOF):m/z=1331.6(100%)[M
+](calcd.for C
88H
118N
2O
8:1331.89)。
Fig. 8 be its proton nmr spectra (
1hNMR) figure, Fig. 9 be its carbon-13 nmr spectra (
13cNMR) figure, Figure 10 are its mass spectrum (MS) figure.
Embodiment 2
1,1,7-bis-(3 ', 4 '-two pentyloxy phenyl)-N, N ' one or two (2-hexyl octyl group)-3,4:9,10-perylene diimides---compound (1)
Adopt two 2-hexyl Gui Ji perylene diimide (9.97g, 10mmol) of 1,7-dibromo, Pd(PPh
3)
4(four (triphenylphosphine) network palladium, 1.2g, 1mmol), toluene (160ml), 2M Na
2cO
3solution (40ml), 3,4-bis-pentyloxy phenylo boric acid (6.4g, 2.2mmol), methyl alcohol (60mml), method prepares compound (A) with in embodiment 1 step 1, and productive rate 80%, Mp. is: 90.8-92.6 DEG C.
By hydrogen nuclear magnetic resonance spectrum analysis, concrete data are:
1hNMR (CDCl
3) δ: 0.951(t, 12H, CH
3), 0.977(t, 6H, CH
3), 0.995(t, 6H, CH
3), 1.24-1.47(m, 62H, CH
2), 1.76(m, 4H, CH
2), 1.88(m, 4H, CH
2), 1.92(m, 4H, CH
2), 3.88 (m, 4H, NCH
2), 4.05-4.16 (m, 8H, OCH
2), 6.92(m, 6H, ArH), 7.90(d, 2H, PerH), 8.17(d, 2H, PerH) and, 8.61(s, 2H, Per-H).Its proton nmr spectra (
1hNMR) as shown in figure 11.
2,1,7-bis-(3,3 ', 4,4 '-two amyl phenyl ether) cool-N, N '-two (2-hexyl octyl group) imide (2)
Adopt compound (1) (1.33g, 1mmol), methylene dichloride (90mml), methylsulfonic acid (10mml), DDQ(DDQ, 0.73g), method prepares compound (B) with in embodiment 1 step 2, and productive rate 90%, Mp. is: 256.6-257.7 DEG C.
By proton nmr spectra, carbon-13 nmr spectra and mass spectroscopy, the product finally obtained, concrete data are: 1HNMR (CDCl
3) δ: 0.787(t, 12H, CH
3), 0.803(t, 6H, CH
3), 0.819(t, 6H, CH
3), 1.147-1.552(m, 56H, CH
2), 1.193 (m, 10H, CH
2), 2.271-2.306(m, 8H, CH
2), 4.273 (m, 4H, NCH
2), 4.585 (t, 4H, OCH
2), 4.877(t, 4H, OCH
2), 8.449(m, 4H, ArH), 9.766(s, 4H, PerH).
13CNMR(75MHz，CDCl
3)：δ164.59,151.03,126.14,124.37,123.94,121.12,121.09,120.97,120.13,104.82,69.26,44.61,36.89,31.99,31.89,31.82,30.16,29.87,29.68,29.60,29.42,29.32,28.86,26.64,22.92,22.66,22.56,14.26,14.02,13.96.MS(MALDI-TOF):m/z=1331.5(100%)[M+](calcd.for C
88H
118N
2O
8:1331.89)。
Figure 12 be its proton nmr spectra (
1hNMR) figure, Figure 13 be its carbon-13 nmr spectra (
13cNMR) figure, Figure 14 are its mass spectrum (MS) figure.
Embodiment 3
1,1,7-bis-(3 ', 4 '-two pentyloxy phenyl)-N, N ' one or two (1-butyl undecyl)-3,4:9,10-perylene diimides---compound (3)
Adopt two 1-butyl Shi mono-Wan Ji perylene diimide (9.97g, 10mmol) of 1,7-dibromo, Pd(PPh
3)
4(four (triphenylphosphine) network palladium, 1.2g, 1mmol), toluene (160ml), 2M Na
2cO
3solution (40ml), 3,4-bis-pentyloxy phenylo boric acid (6.4g, 2.2mmol), methyl alcohol (60mml), method prepares compound (A) with in embodiment 1 step 1, and productive rate 80%, Mp. is: 115.5-118.2 DEG C.
By hydrogen nuclear magnetic resonance spectrum analysis, concrete data are:
1hNMR (CDCl
3) δ: 0.85(t, 12H, CH
3), 0.87(t, 6H, CH
3), 1.02(t, 6H, CH
3), 1.22-1.85(m, 68H, CH
2), 1.93(m, 4H, CH
2), 2.26(m, 4H, CH
2), 3.99 (t, 4H, OCH
2), 4.08 (t, 4H, OCH
2), 5.15(m, 2H, NCH), 6.99(s, 2H, ArH), 7.09(m, 4H, ArH) and, 7.94(d, 2H, PerH), 7.96(d, 2H, PerH) and, 8.630(s, 2H, PerH).Its proton nmr spectra (
1hNMR) as shown in figure 15.
2,1,7 two (3,3 ', 4,4 '-two amyl phenyl ether) cool-N, N '-two (1-butyl undecyl) imide---compound (4)
Adopt compound (3) (1.33g, 1mmol), methylene dichloride (90mml), methylsulfonic acid (10mml), DDQ(DDQ, 0.73g), method prepares compound (B) with in embodiment 1 step 2, and productive rate 90%, Mp. is: 278.2-282.7 DEG C.
By proton nmr spectra, carbon-13 nmr spectra and mass spectroscopy, the product finally obtained, concrete data are:
1h NMR (CDCl
3) δ: 0.76(t, 12H, CH
3), 0.77(t, 6H, CH
3), 0.792(t, 6H, CH
3), 1.03-1.83(m, 62H, CH
2), 2.27(m, 12H, CH
2), 2.62(m, 4H, CH
2), 4.61 (m, 8H, OCH
2), 5.48(m, 2H, NCH), 8.26(s, 4H, ArH), 9.64(d, 4H, PerH).
13CNMR(75MHz，CDCl
3)δ：165.30，164.38，151.04，126.12，123.97，123.50，121.62，120.80，120.64，119.88，105.00，69.38，55.17，32.85，32.59，31.84，29.90，29.84，29.77，29.73，29.65，29.39，29.30，29.05，28.55，28.37，27.78，22.95，22.81，22.57，14.29，14.26，14.11，13.99。MS(MALDI-TOF):m/z=1331.5(100%)[M
+](calcd.for C
88H
118N
2O
8:1331.89)。
Figure 16 be its proton nmr spectra (
1hNMR) figure, Figure 17 be its carbon-13 nmr spectra (
13cNMR) figure, Figure 18 are its mass spectrum (MS) figure.
Prepared by the present invention can be widely used in electron device containing the cool compound of sub-amides dibenzo.As semiconductor material, can be used as the active component of Organic Light Emitting Diode (OLED), field effect transistor (FET) and solar cell.Compared with other liquid crystal unit, larger aromatic series rigid nuclear is had containing the cool liquid crystal molecule of sub-amides dibenzo, more large-area mutual superposition can be formed between adjacent aromatic nucleus, there is higher carrier mobility, and there is high-sequential columnar arrangement and good solvability, be conducive to its application in the devices.
Claims (2)
1. a preparation method for the cool compounds of dibenzo, is characterized in that comprising following concrete steps:
(1) 1,7-bis-(3 ', 4 '-dialkoxy phenyl)-N, N '-bis-(alkyl)-3,4:9,10-perylene diimides
At N
2under environment, by Pd (PPh
3)
4toluene solution add the round-bottomed flask that 1,7-dibromo Shuan Wan Ji perylene diimide is housed, then add 2M Na
2cO
3the CH of solution and 3,4-dialkoxy phenylo boric acid
3oH solution, stirs 48 hours at 70 DEG C; Be cooled to room temperature, add NH
3water and 2N Na
2cO
3solution termination reaction, CHCl
3extraction, washing, anhydrous Na
2sO
4drying, filters, boils off most of solvent, add methanol extraction, from CHCl
3dark blue powder is obtained with recrystallizing methanol;
(2) 1,7-bis-(3,3 ', 4,4 '-dialkoxy benzene) cool-N, N '-two (alkyl) imide
By 1,7-bis-(3 ', 4 '-dialkoxy phenyl)-N, N '-bis-(alkyl)-3,4:9,10-perylene diimides is dissolved in the there-necked flask filling anhydrous methylene chloride and methylsulfonic acid, mixture is cooled to 0 DEG C, adds DDQ three times every five minutes points, react and control progress by TLC, react 30 minutes, then add ice methyl alcohol cancellation reaction, filtering precipitate, then carry out separating-purifying by chromatographic column, the impurity of removing initial point, obtains red solid by methylene dichloride and recrystallizing methanol.
2. the preparation method of the cool compounds of dibenzo according to claim 1, is characterized in that: in step (1), after adding methanol extraction, first purifies with silicagel column, then from CHCl
3and recrystallizing methanol.
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