EP2925817A2 - Aminosubstituierte peri-arylenfarbstoffe - Google Patents
Aminosubstituierte peri-arylenfarbstoffeInfo
- Publication number
- EP2925817A2 EP2925817A2 EP13811806.2A EP13811806A EP2925817A2 EP 2925817 A2 EP2925817 A2 EP 2925817A2 EP 13811806 A EP13811806 A EP 13811806A EP 2925817 A2 EP2925817 A2 EP 2925817A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- atoms
- radicals
- replaced
- groups
- independently
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 125000003277 amino group Chemical group 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 81
- 229910052739 hydrogen Inorganic materials 0.000 claims description 110
- 125000004432 carbon atom Chemical group C* 0.000 claims description 103
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 101
- -1 9,10-disubstituted anthracene residues Chemical group 0.000 claims description 63
- 125000000217 alkyl group Chemical group 0.000 claims description 44
- 229910052757 nitrogen Inorganic materials 0.000 claims description 39
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 33
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 33
- 125000003748 selenium group Chemical group *[Se]* 0.000 claims description 33
- 125000004434 sulfur atom Chemical group 0.000 claims description 32
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical group [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 32
- 229910052794 bromium Inorganic materials 0.000 claims description 28
- 239000000460 chlorine Substances 0.000 claims description 28
- 229910052731 fluorine Inorganic materials 0.000 claims description 28
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 28
- 229910052740 iodine Inorganic materials 0.000 claims description 28
- 229910052801 chlorine Inorganic materials 0.000 claims description 27
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 239000011630 iodine Substances 0.000 claims description 23
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 22
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 22
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 22
- 239000011737 fluorine Substances 0.000 claims description 22
- 229910052736 halogen Inorganic materials 0.000 claims description 22
- 150000002367 halogens Chemical class 0.000 claims description 22
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 21
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 13
- 125000001424 substituent group Chemical group 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 4
- 241000605059 Bacteroidetes Species 0.000 claims 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 27
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 238000000862 absorption spectrum Methods 0.000 abstract description 8
- GGVMPKQSTZIOIU-UHFFFAOYSA-N quaterrylene Chemical group C12=C3C4=CC=C2C(C2=C56)=CC=C5C(C=57)=CC=CC7=CC=CC=5C6=CC=C2C1=CC=C3C1=CC=CC2=CC=CC4=C21 GGVMPKQSTZIOIU-UHFFFAOYSA-N 0.000 abstract description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 70
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 239000000741 silica gel Substances 0.000 description 32
- 229910002027 silica gel Inorganic materials 0.000 description 32
- 239000007787 solid Substances 0.000 description 19
- 238000005481 NMR spectroscopy Methods 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 238000006467 substitution reaction Methods 0.000 description 15
- 238000004440 column chromatography Methods 0.000 description 14
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 14
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 14
- 239000007850 fluorescent dye Substances 0.000 description 13
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- BIGSSBUECAXJBO-UHFFFAOYSA-N terrylene Chemical group C12=C3C4=CC=C2C(C=25)=CC=CC5=CC=CC=2C1=CC=C3C1=CC=CC2=CC=CC4=C21 BIGSSBUECAXJBO-UHFFFAOYSA-N 0.000 description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 239000003086 colorant Substances 0.000 description 8
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 8
- 231100000489 sensitizer Toxicity 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- WLLGXSLBOPFWQV-UHFFFAOYSA-N MGK 264 Chemical compound C1=CC2CC1C1C2C(=O)N(CC(CC)CCCC)C1=O WLLGXSLBOPFWQV-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 125000005605 benzo group Chemical group 0.000 description 6
- 230000007717 exclusion Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- LBOJSACZVLWUHN-UHFFFAOYSA-N perylene-3,4-dicarboximide Chemical compound C=12C3=CC=CC2=CC=CC=1C1=CC=C2C(=O)NC(=O)C4=CC=C3C1=C42 LBOJSACZVLWUHN-UHFFFAOYSA-N 0.000 description 6
- 229920000297 Rayon Polymers 0.000 description 5
- 239000012327 Ruthenium complex Substances 0.000 description 5
- 239000000976 ink Substances 0.000 description 5
- 239000004922 lacquer Substances 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000010981 turquoise Substances 0.000 description 5
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 4
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical class B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 4
- 210000004209 hair Anatomy 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- XQFGVGNRDPFKFJ-UHFFFAOYSA-N 1,2,3,5,6,7-hexahydropyrrolo[1,2-b]pyridazine Chemical compound N1CCC=C2CCCN21 XQFGVGNRDPFKFJ-UHFFFAOYSA-N 0.000 description 3
- SURCGQGDUADKBL-UHFFFAOYSA-N 2-(2-hydroxyethylamino)-5-nitrobenzo[de]isoquinoline-1,3-dione Chemical compound [O-][N+](=O)C1=CC(C(N(NCCO)C2=O)=O)=C3C2=CC=CC3=C1 SURCGQGDUADKBL-UHFFFAOYSA-N 0.000 description 3
- QGNQEODJYRGEJX-UHFFFAOYSA-N 4h-isoquinoline-1,3-dione Chemical compound C1=CC=C2C(=O)NC(=O)CC2=C1 QGNQEODJYRGEJX-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000000732 arylene group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- JVURVJHBFHCOQX-UHFFFAOYSA-N perylene-3,4-dicarboxylic acid Chemical compound C=12C3=CC=CC2=CC=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O JVURVJHBFHCOQX-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229960005235 piperonyl butoxide Drugs 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002964 rayon Substances 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- FXNJNGMYIZRQRG-UHFFFAOYSA-N tridecan-7-amine Chemical compound CCCCCCC(N)CCCCCC FXNJNGMYIZRQRG-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DFXXKJOOIOTWDX-UHFFFAOYSA-N 1,4-dibromoperylene Chemical group C=12C3=CC=CC2=CC=CC=1C1=C(Br)C=CC2=C1C3=CC=C2Br DFXXKJOOIOTWDX-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 244000198134 Agave sisalana Species 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 2
- 240000000491 Corchorus aestuans Species 0.000 description 2
- 235000011777 Corchorus aestuans Nutrition 0.000 description 2
- 235000010862 Corchorus capsularis Nutrition 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000219146 Gossypium Species 0.000 description 2
- 240000006240 Linum usitatissimum Species 0.000 description 2
- 235000004431 Linum usitatissimum Nutrition 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- GRSMWKLPSNHDHA-UHFFFAOYSA-N Naphthalic anhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=CC3=C1 GRSMWKLPSNHDHA-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 235000009120 camo Nutrition 0.000 description 2
- 235000005607 chanvre indien Nutrition 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
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- 238000004043 dyeing Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 239000011487 hemp Substances 0.000 description 2
- 238000004896 high resolution mass spectrometry Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
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- 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 description 2
- JQQSUOJIMKJQHS-UHFFFAOYSA-N pentaphene Chemical group C1=CC=C2C=C3C4=CC5=CC=CC=C5C=C4C=CC3=CC2=C1 JQQSUOJIMKJQHS-UHFFFAOYSA-N 0.000 description 2
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
- C09B5/62—Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series
-
- 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
- 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
- C07D471/12—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 three hetero rings
- C07D471/16—Peri-condensed systems
-
- 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
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- 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
- Y02E10/52—PV systems with concentrators
-
- 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
- Y02E10/542—Dye sensitized solar cells
-
- 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
Definitions
- the present invention relates to Jen-arylene dyes, in particular terrylene and Quaterrylenfarbstoffe carrying amino groups.
- Such compounds can be prepared under mild reaction conditions. Due to their absorption spectra, they are suitable for applications in the field of solar energy, in particular as sensitizers in Grätzel solar cells.
- Terrylene color substances such as terrylene-3,4: 9,10-tetracarboxylic bisimides (1)
- H. Langhals, A. Hofer, DE 10201 1018815 are preferred as higher homolys of the perylene dyes
- C H. Langhals, Heterocydes 1995, 40, 477-500
- the ⁇ '-substituents in compounds of type (1) have only insignificant effects on the UV / Vis spectra due to the presence of orbital nodes in the HOMO and LUMO on these atoms. They are suitable for controlling further properties of the substances, such as the solubility.
- Sec-alkyl radicals such as the 1 -hexylheptyl radical (compare Compound 1a, FIG. 1) or the 1-nyldecyl radical have proven to be extremely effective here and lead to deep blue, strongly red fluorescent solutions of (1) in lipophilic Media. Because of their photochemical stability and strong fluorescence, the substances are basically of interest for solar applications.
- the object of the present invention was therefore to provide organic compounds which are synthetically readily accessible and light-fast, and which exhibit efficient light absorption in a suitable wavelength range, e.g. be used as sensitizers for dye-sensitized solar cells (Grätzel cells) without having to be complexed with metals.
- amino / ⁇ -arylenes because of their absorption spectra, are well suited for use in the production of solar energy.
- perylenetetracarboxylic bisamides but also terrylenetetracarboxylic bisimides (hereinafter also referred to as Terryl enbi simide), such as Compound (1), or quaterrylenetetracarboxylic bisimides (hereinafter also referred to as Qu aterrylenbi simide), such as Compound (2), are simple Substitute with. Amines to obtain amino-substituted dyes.
- ammoeri-arylene dyes (eg compounds (14) - (17) see Fig. 4) show advantageous absorption spectra, which allow a variety of applications. Because of the long wavelength spectral range of absorption they are of particular interest for the production of solar energy, for example in photovoltaics, for example as an adjuvant in barrier photovoltaic cells or as metal-free sensitisers for the Grätzel cell. There they can reach and even exceed the efficiency of known metal complexes.
- the present invention particularly provides the following embodiments.
- n 1 or 2
- X is a radical R 12 or a radical -NR 5 R 6
- the radicals R 1 to R 18 may be the same or different from each other and independently of one another hydrogen or linear alkyl radicals having at least one and at most 37 represent C atoms in which one to 10 CH 2 units can be replaced independently of each other by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-Cti-CH ⁇ groups, in which an H unit also may be replaced by a nitrogen atom
- acetylenic C C-Grappen, 1,2-, 1, 3- or 1, 4-substituted phenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3 , 4- or 3,5-disubstituted pyridine, 2,3-, 2,4-, 2,5- or 3,4-di-substituted thiophene, 1, 2, 1, 3, 1, 4, 1 , 5-
- Up to 12 individual hydrogen atoms of the CI F groups of the alkyl radicals can each independently be replaced by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains with up to 18 C atoms; also in these alkyl chains, one to 6 CH : -F.inomme can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or Iran - CH ⁇ C 1 1 1 -G-pen, in which a CH- Unit may also be replaced by a nitrogen atom, acetylenic CsC groups 1, 2, 1, 3 or 1, 4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,
- the free valences of the methine groups or the quaternary carbon atoms can be linked in pairs, so that rings arise, such. Cyclohexane rings.
- amino-arylene compounds of the following formulas (IVa) and (IVb) are provided:
- Another embodiment of the invention relates to a process for preparing a compound of formula (I) or of formulas (IVa) or (IVb), characterized in that a corresponding ene-arylene is reacted with a primary or secondary amine.
- radicals R to R 4 and R are independently defined as R 1 in formula (1), and the radicals R 8 to R 14 and R 2j to R 27 are independently defined as R 8 in formula (I); in a photovoltaic solar cell.
- the invention also relates to a photovoltaic solar cell containing a compound of the formula (V), the formula (IV 7 a) or the formula (IVb) as defined above.
- the compounds of the invention having a terrylene or quaternary structure have the following formula (I):
- the compounds of the formula (1) are preferably a compound selected from compounds of the formulas (IIa), (IIb), (IIIa) or (IIIb):
- n 1 or 2
- X is a radical R i2 or a radical -NR 5 R 6 .
- Up to 12 individual hydrogen atoms of the CTE groups can each independently be replaced on the same carbon atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group, or by a linear alkyl chain with up to 18 carbon atoms.
- R 1 or R 2 are alkyl radicals, in particular secondary alkyl radicals. Particularly preferred are the 1-hexylheptyl or the 1-Nylyldecylrest.
- Up to 12 individual hydrogen atoms of the CH 2 groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group, or by a linear alkyl chain with up to 18 carbon atoms.
- the free valences of the methine groups or of the quaternary C atoms can be linked in pairs, so that rings are formed, such as, for example, Cyclohexane.
- R 3 and R 4 or R and R 6 are preferably alkyl radicals, or in each case one of R 3 and R 4 or R 5 and R 6 is an alkyl radical, and the other is hydrogen.
- R 3 and R 4 or R 5 and R 6 are an alkyl radical, and the other is hydrogen.
- formulas formulas (I), (IIa), (IIb), (IIIa) and (IIIb) form R 3 and R 4 or R 5 and R 6 together with the nitrogen atom to which they are bound, a pyrrolidine ring.
- Particularly preferred is the variant according to which R 3 and R 4 or R 3 and R 6 together with the nitrogen atom to which they are attached form a pyrrolidine ring.
- the radicals R x to R " are identical or different and can independently of one another denote hydrogen, the halogen atoms F, CL Br or I, or linear alkyl radicals having at least one and at most 37 C atoms, in which one to 10 CH units are independent can be replaced by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or in-methyl groups in which a CH unit can also be replaced by a nitrogen atom, acetylenic CsC groups, 1, 2 , 1, 3 or 1, 4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8 -, 2,3-, 2,6- or 2,7-disubsti
- Up to 12 individual hydrogen atoms of the CH 2 groups of the alkyl radicals can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains having up to 18 carbon atoms; Also in this alkyl chain may have a C H to 6-healing independently be replaced by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or // • (/ "v-CH- H groups, in which a CH Unit may also be replaced by a nitrogen atom, acetylenic C ⁇ C groups 1, 2, 1, 3 or 1, 4-substituted phenyl, 2,3-, 2,4-, 2,5-, 2,6 , 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1, 2, 1, 3,
- the free valences of the methine groups or of the quaternary C atoms can be linked in pairs, so that rings are formed, such as, for example, Cyclohexane.
- radicals R ⁇ R '°, R 15 and R 16 in the formula (I) may have different meanings within the definitions given above in each occurrence.
- the radicals R ' in formula (IIb), R to R * ⁇ in formula (IIIa) and R' to R 21 in formula (IIIb) are not the halogen atoms F, Cl, Br or I.
- the radicals R to R ⁇ ⁇ are hydrogen.
- a CHi moiety of an alkyl group or an alkyl chain which can be replaced by definition may also be a terminal moiety in an alkyl group of an alkyl chain, ie, a corresponding formal CH 2 moiety a -CH 3 group act. Accordingly, this applies to the methine groups, which can be linked in pairs so that rings are formed. These methine groups may also each be a formal CH moiety present within a CH 2 group or CH 3 group and additionally having a free valence to form a ring having a second corresponding group.
- the quaternary C atoms which may be linked in pairs, may result if, for a CH 2 group, a monovalent substituent has already replaced a hydrogen atom and, in addition, a free valence is present to form a ring with a second corresponding group.
- Up to 12 individual hydrogen atoms of the CH 2 groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group, or by a linear alkyl chain having up to 18 carbon atoms.
- each independently of one another also be replaced by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains having up to 18 C atoms; also in these alkyl chains, one to 6 CH 2 units can be replaced independently of one another by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-C HC H -glys, in which a CH unit is also replaced by a nitrogen atom acetylenic Cs groups may be 1, 2, 1,3 or 1,4-substituted phenyl, 2,3, 2,4, 2,5, 2,6, 3,4 or 3 , 5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1, 3, 1, 4, 1, 5, 1, 6-, 1-,
- the free valences of the methine groups or of the quaternary C atoms can be linked in pairs, so that rings are formed, such as, for example, Cyclohexane.
- R 1 or R 2 are alkyl radicals, in particular secondary alkyl radicals. Particularly preferred are the 1 -hexylheptyl or the 1-Nylyldecylrest.
- the radicals R ⁇ R 4 and R are the same or different, and can represent at least one and not more than 37 C atoms, in which one to 10 CH 2 units may be replaced independently of one another in each case by carbonyl groups are independently hydrogen or linear alkyl, Oxygen atoms, sulfur atoms, selenium atoms. Tellurium atoms, cis- or in which a CH unit can also be replaced by a nitrogen atom, acetylenic CsC groups, 1, 2, 1, 3 or 1, 4-substituted phenyl radicals,
- Up to 12 individual hydrogen atoms of the CH 2 groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group, or by a linear Alkvlkctte having up to 18 carbon atoms.
- acetylenic CsC groups 1, 2, 1, 3 or 1, 4-substituted phenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5 disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals 1, 2, 3, 3, 1, 4, 1, 5, 1, 6-, 1-, 7-, 1-, 8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1, 2-, 1.3-, 1, 4, i, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2, 3, 2,6-, 2,7-, 2,9-
- R 3 and R 4 are alkyl radicals, or one of R J and R 4 is an alkyl radical and the other is hydrogen.
- R 'and R 4 together with the nitrogen atom to which they are attached form a pyrrolidine ring.
- R is preferably hydrogen or an alkyl radical, in particular hydrogen.
- Up to 12 individual hydrogen atoms of the CHi groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or loci or the cyano group, or by a linear alkyl chain with up to 18 C atoms.
- Up to 12 individual hydrogen atoms of the CH 2 groups of the alkyl radicals can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains having up to 18 carbon atoms; also in these alkyl chains, one to 6 CH 2 units can be replaced independently of one another by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-I-11-fluorophenyl.
- acetylenic C ⁇ C groups 1, 2-, 1, 3- or 1,4-substituted phenyl, 2,3-, 2,4-, 2,5 , 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3- , 1, 4, 1, 5, 1,6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-disubstituted naphthalene radicals having one or two carbon atoms 1, 2, 3, 1 2,3-, 2,6-, 2,7-. 2,9-, 2,10- or 9,10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms.
- the free valencies of the methine clusters or of the quaternary C atoms can be linked in pairs, so that rings are formed, such as, for example, Cyclohexane.
- the radicals R 8 to R 14 and R 2j to R 2 ' are preferably hydrogen.
- Particularly preferred compounds of the formulas (IVa) and (IVb) are the following compounds (19) and (20):
- Fig. 6 shows that UV / Vis absorption spectrum of the terrylene bisimide Ia (see Fig. 4) compared to the spectra of amino substituted compounds.
- a simple substitution with a pyrrolidine unit (14) leads to a bathochromic shift with weakening of the vibrational structure; Green solutions are obtained.
- the second substitution to 15 causes another bathochromic shift; the substance forms deep blue solutions.
- the UV / Vis absorption of the quaterrylene biosimple 2a depicted in FIG. 7 depicted in FIG. 7 (see FIG.
- a further embodiment of the invention relates to the use of a compound of the following formula (V) or of the formulas (IVa) or (IVb), as defined above, in a photovoltaic solar cell.
- m is 0, 1 or 2.
- the variables or radicals X and R to R are independently defined as the variables or radicals X and R 1 to R i for compounds of formula (I).
- the compound of formula (V) is a compound of formula ( ⁇ ), more preferably a compound of formula (IIa), (ITb), (Ufa) or (Ilfb) as defined above.
- the compound (14), (15), (16), (17), (19) or (20) is used in a photovoltaic solar cell.
- Further preferred compounds of the formula (V) for use in a photovoltaic solar cell are amino-perylenebisimides of the formulas (Via) and (VIb).
- radicals R 1 and R " are identical or different and can be independent of one another
- Nitrogen atoms can be replaced. Up to 12 individual hydrogen atoms of the CH 2 groups can each independently be replaced on the same carbon atoms by the halogens fluorine, chlorine, bromine or iodine or the vano group, or by a linear alkyl chain having up to 18 carbon atoms.
- Up to 12 individual hydrogen atoms of the CH 2 groups of the alkyl radicals can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains having up to 18 carbon atoms; also in these alkyl chains, one to 6 CH 2 units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or in which a CH unit may also be replaced by a nitrogen atom, acetylenic Cs groups 1, 2, 1, 3 or 1, 4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3, 5 -di-substituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3,
- the free valences of the methine groups or of the quaternary C atoms can be linked in pairs, so that rings are formed, such as, for example, Cyclohexane.
- R 1 or R ⁇ are alkyl radicals, in particular secondary alkyl radicals. Particular preference is given to the 1-hexylheptyl radical or the 1-nonyldecyl radical.
- the radicals R ⁇ R 4, R 5 and R 6 are the same or different, and may represent atoms in which one to 10 CE ⁇ units may be replaced independently of one another are each independently hydrogen or linear alkyl radicals having at least one and not more than 37 C by each carbonyl groups.
- Ci F groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group, or by a linear alkyl chain with up to 18 ( " -Atomen.
- one to 6 CH; -F.inomme may be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or in which a CH unit can also be replaced by a nitrogen atom, acetylenic CsC groups, 1, 2, 1, 3 or 1, 4-substituted phenyl radicals, 2,3-, 2,4-, 2,5- , 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1, 2, 1, 3, 1, 4-, 1, 5-, 1, 6-, 1, 7-, 1, 8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals, wherein one or zw r ei carbon atoms may be replaced by nitrogen atoms, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7,
- the free valences of the methine groups or of the quaternary C atoms can be linked in pairs, so that rings are formed, such as, for example, Cyclohexane.
- R 'and R 4 or R 5 and R 6 are preferably alkyl radicals, or in each case one of R 3 and R 4 or R '" and R 6 is an alkyl radical, and the other is hydrogen in the formulas (IVa) and (IVb) R 'and R 4 or R 5 and R 6 together with the nitrogen atom to which they are attached form a pyrrolidine ring, particular preference is given to the variant according to which R J and R 4 and R 3 and R 6 together with the nitrogen atom to which they are attached form a pyrrolidine ring.
- the radicals R 8 to R ! 4 are identical or different and can independently of one another denote hydrogen, the halogen atoms F, Cl, Br or 1, or linear alkyl radicals having at least one and at most 37 C atoms, in which one to 10 CH 2 Units can be replaced independently by each carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms.
- Up to 12 individual hydrogen atoms of the CH 2 groups of the alkyl radicals can each independently be replaced on the same carbon atom by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains having up to 18 carbon atoms; Also in these Aikyi chains, one to six CTF units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans -CHC H groups.
- acetylenic C ⁇ C groups 1, 2, 1, 3 or 1, 4-substituted phenyl, 2,3-, 2,4-, 2,5 , 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms are represented by nitrogen atoms 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2 can be replaced , 3, 2, 6, 2, 7, 2, 9, 2, 10 or 9, 10 disubstituted anthracene radicals in which one or two carbon atoms may be replaced by nitrogen atoms.
- the free valences of the methine groups or of the quaternary carbon atoms can be linked in pairs, so that rings are formed, such as, for example.
- the radicals R s to R 14 are hydrogen.
- Particularly preferred compounds of the formulas (VIa) and (VIb) for use in solar cells are the following compounds (32) to (37):
- the compounds of the formula (IVa), (IVb) and (V) in solar cells serve in particular as light absorbers. These compounds can be used as individual compounds or as a mixture of two or more of these compounds.
- a photovoltaic solar cell employing a compound of the formula (IVa), (IVb) or (V) is preferably a purely organic junction cell or Grätzel cell, more preferably a Grfordcl cell, and more preferably a Grätzel cell that a layer containing titanium dioxide nanoparticles.
- Preferred compounds for use in a photovoltaic solar cell are the compounds of the formulas (IIa), (IIb), (IIIa), (IIIb), (Via) or (VIb) defined above, in particular one of the compounds (14) to (17) or (32) to (37), more preferably of the formulas (IIa), (IIb), (IIIa) or (IIIb), especially one of the compounds (14) to (17).
- the invention also relates to a photovoltaic solar cell containing a compound of formula (IVa), (IVb) or (V).
- the solar cell is preferably a purely organic junction cell or a Grätzel cell, more preferably a Grätzel cell, and more particularly a Grätzel cell containing a layer of titanium dioxide nanoparticles.
- the compound of the formula (IVa), (IVb) or (V) is preferably a compound of the formula (IIa), (IIb), (IIIa), (IIIb), (Via) or (VIb), in particular one of the compounds (14) to (17) or (32) to (37), more preferably of the formulas (IIa), (IIb), (IIIa) or (IIIb), especially one of the compounds (14) to (17 ).
- pigments and colorants for dyeing purposes, also for decorative and artistic purposes, such as for example glue colors, watercolor paints, water colors, colors for inkjet printers, paper inks, printing inks, inks and inks and other colors for painting and writing Z. awake and in paints.
- coloring natural substances for example paper, wood, straw or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, flax or their conversion products such as viscose fiber, nitrate silk or copper rayon (rayon)
- mordant dyes eg for coloring natural products
- examples are paper, wood, straw, or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, flax or their conversion products such as viscose, nitrate silk or copper rayon (Reyon).
- Preferred salts for pickling are aluminum, chromium and iron salts, g) use as an additive to other colors in which a certain shade of shade is to be achieved, particularly bright shades are preferred. h) Use for marking, security and display purposes, especially taking into account their fluorescence, such as dyes or fluorescent dyes for signal colors, preferably for visual highlighting lettering and drawings or other graphic products, for marking signs and other objects and in display elements , including passive display elements, traffic signs and traffic lights i) use for security markings, wherein the high chemical and photochemical stability and possibly also the fluorescence of the substances is advantageous, preferably for
- j) use as fluorescent dyes for machine-readable markings, preferred are alphanumeric imprints or barcodes.
- k) Use as dyes in inkjet printers in homogeneous solution, preferably as a fluorescent ink. 1) Use as dyes or fluorescent dyes in display, illumination or image converter systems in which the excitation by electrons, ions or UV radiation takes place, for example in fluorescence displays, Braun tubes or in fluorescent tubes, m) use as a tracer, for example in biochemistry , Medicine, technology and natural sciences, here, the dyes may be covalently linked to substrates or via secondary valences, such as hydrogen bonds or hydrophobic interactions (adsorption).
- n) Use as dyes or fluorescent dyes in chemiluminescence systems, for example in chemiluminescent light rods, in luminescence immunoassays or other luminescence detection methods.
- o) Use as a material for leak testing of closed systems.
- p) Use as functional materials, such as in data storage, preferably in optical storage, such as the CD or DVD disks, in OLEDS (organic light-emitting diodes).
- q) Use as pigments in electrophotography: eg for dry copying systems (Xerox process) and laser printers ("Non Impact Printing").
- r Use for the frequency conversion of light, eg to make shortwave light of longer wavelength, visible light (s) used as a starting material for superconductive organic materials, (t) used as fluorescent dyes in scintillators, (u) used as dyes or fluorescent dyes in optical light harvesting systems, such as the fluorescent solar panel or fluorescence activated displays, (v) use in liquid crystals to redirect light (w) used as dyes or fluorescent dyes in cold light sources (x) for use in light - induced polymerisation for the synthesis of plastics y) used as dyes or fluorescent dyes for materials testing, eg in the manufacture and testing of semiconductor and semiconductor devices oreszenzfarbstoffe in photoconductors. aa) Use as dyes or fluorescent dyes in photographic processes.
- Quaterrylenebisimides 2 can, as illustrated in FIG. 2, also have been prepared from the perylene-3,4: 9, 10-tetracarboxylic bisanhydride (3), which has been reacted analogously to the dicarboximide (5) to brominate (7) (L. Feiler, Langhals, K. Polborn, Liebigs Ann. Chem. 1995, 1229-1244) and then using a Pd catalyst was linked CC-. Ring closure of (8) can be achieved under the conditions of the Sakamoto reaction (supra).
- the corresponding perylene-3,4: 9,10-tetracarboxylic anhydride imide (9) can be C-C linked directly using decarboxylating copper.
- perylene-3,4-dicarboximide (4) is brominated and then - as already described - C-C linked and cyclized.
- the combination of the two ways is very economical in terms of starting materials.
- perylene with N-bromosuccinimide can be brominated to the dibromo derivative (10) and reacted with bispinacol borane to give the diboron derivative (11) ((a) Y. Avlasevich, K. Müllen, J. Org. Chem. 2007, 72, 10243-10246 (b) A. Suzuki, N. Miyaura, M. Murata, T. Ishiyama, J. Am. Chem. Soc. 1993, 115, 1 1018-1 1020.
- terrylenebisimides such as compound (1)
- quaterrylenebisimides such as compound (2)
- amines react with amines.
- a smooth reaction according to Figure 4 of la and also of 2a with pyrrolidine was found at room temperature; although terrylene and Quaterrylenbisimide are chemically pronounced resistant substances, for example, against caustic soda or hydrochloric acid. Pyrrolidine units were introduced into the o-positions relative to the carbonyl groups as a result of this reaction.
- perylene bisimides to 21 and 22 is known (H. Langhals, S. Christian, DE 10201 1 1 16207), however, compounds of T ps (1) and (2) are more electron-rich than perylenebisimides, and the attack of an amine would have been considered much less likely.
- a further aspect of the invention relates to a process for the preparation of the compounds of the aforementioned formulas (I), (IVa) or (TVb), in particular the compounds of the above formulas (IIa), (IIb), (IIIa), (Illb ), (IVa) or (TVb), which is characterized in that a peri-arylene is reacted with a primary or secondary amine.
- Vn-arylenes as starting compounds for reaction with an amine are shown below by way of illustration.
- the reaction of the peri-arylene with the primary or secondary amine preferably takes place in a concentrated solution of the amine.
- a liquid amine itself may also be used as the reaction solvent. Pyrrolidine is therefore particularly preferred as the amine.
- the reaction temperature is not particularly limited, preferably For example, the reaction takes place at temperatures between -20 and 100 ° C, more preferably at temperatures between 15 and 50 ° C, most preferably at room temperature.
- IR Spectra Perkin Elmer 1420 Ratio Recordmg Infrared Spectrometer, FT 1000: UV / Vis Spectra: Van to Gary 5000 and Bruins Omega 20; Fluorescence spectra: Varian Eclispe: NMR Spectroscopy: Varian Vnmrs 600 (600 MHz); Mass spectrometry: Finnigan MAT 95. Fluorescence quantum yields were determined analogously to H. Langhals, J. Karolin, L. B.-A. Johansson, J. Chem. Soc., Faraday Trans. 1998, 94, 2919-2922; reference dye S-13 is / V V-bis-1-hexylheptylperylene-3,4: 9, 10-tetracarboxylic bisimide, RN 1 10590-84-6.
- Hexylheptylamine (5.04 g, 25.1 mmol) and 1, 8-naphthalenedicarboxylic anhydride (5.00 g, 25.2 mmol) were heated in imidazole (12 g) under argon at 130 ° C for 3 h, allowed to cool, with 2 M aqueous HCl (500 mL). added, extracted twice with CHCh, dried (MgS0 4 ), evaporated in a rough vacuum and purified by column chromatography (silica gel 40-63 Lim, CHCyisohexan 1: 1). Y. 6.2 g (65%) yellow oil. R f (silica gel, chlorofoi-m): 0.85.
- IR (ATR): v 3068.0 (w), 2953.5 (s), 2921.6 (s), 2852.6 (s), 1700.8 (s), 1659.7 (s), 1628.1 (m), 1 588.5 (s), 1515.4 ( w), 1463.7 (m), 1435.6 (w), 1397.5 (m), 1372.5 (m), 1339.3 (s), 1236.0 (s), 1 176.1 (w, br), 1093.4 (w), 1071.9 (w) , 1027.7 (w), 879.7 (w), 844.8 (w), 779.9 (s), 720.9 (w), 696.1 cm -1 (w).
- Example 4 2- (1 -non-1-decyl) benzo [3 / Isoquinoline-1,3-dione: 1-Nyldecylamine (7.12 g, 25.1 mmol) and 1, 8-naphthalenedicarboxylic anhydride (5.00 g, 25.2 mmol) were heated in imidazole (12 g) under argon at 130 ° C for 3 h, allowed to cool with 2 M aqueous HCl (500 mL), extracted twice with CHCl 3 , dried (MgSO 4 ), in a rough vacuum evaporated and purified by column chromatography (silica gel 40-63 ⁇ , C HCl isohexane 1: 1). Y.
- IR (ATR): v 2952.9 (w), 2922.0 (m), 2854.1 (m), 1701.9 (s), 1657.8 (vs), 1617.2 (w), 1587.1 (m), 1571 (m), 1506.3 (w ), 1460.3 (m), 1423.1 (w), 1404.2 (m), 1397.2 (m), 1367.4 (w), 1353.5 (m), 1339.2 (vs), 1265.0 (w), 1 237.7 (s), 1323.8 ( w), 1 265.0 (w), 1 104.9 (m), 1088.0 (m), 1042.1 (w), 973.4 (w), 915.5 (), 882.7 (w), 849.3 (m), 827.4 (w), 809.8 (w), 779.2 (vs), 750.1 (s), 723.8 (111), 686.5 (w), 664.4 (w), 652.0 cm “ '(w).
- 1,3-dione (13) In the absence of air (Ar protective gas), 6-bromo-2- (1-hexylheptyl) benzo [Je] isoquinoline-1,3-dione (12, 100 mg, 0.380 mmol) and 1 , 4-Dibromoperylene (10, 83.3 mg, 0.165 mmol) in toluene (15 mL), with 2 aqueous K 2 CO_rLsg. (5 mL) and ethanol (1 mL), heated to 80 ° C, with tetrakis (triphenylphosphine) palladium (0) (10.0 mg 8.65 ⁇ ), stirred for 16 h at 80 ° C, allowed to cool and with the organic phase separated.
- IR (ATR): v 2952.3 (w), 2923.0 (m), 2854.5 (w), 1697.0 (s), 1655.2 (vs), 161 5.4 (w), 1586.7 (s), 151 1.6 (w), 1455.6 (w), 1398.5 (w), 1391.7 (w), 1344.5 (vs), 1266.7 (w), 1237.9 (s), 1 1 79.1 (w), 1 163.9 (w), 1 1 32.3 (w), 1 103.5 (w), 1072.2 (w), 1034.8 (w), 970.1 (w), 936.5 (w), 862.4 (w), 840.6 (w), 813.5 (m), 784.0 (vs), 771.5 (m), 759.9 (s), 723.9 (w), 701.0 (w), 689.8 cm -1 (w).
- Example 1 A ⁇ ;, -r) i- (l-hexylheptyl) -2-pyrroIidinoterryIen-3,4: 1,12-tetracarboxylic acid bis-l dicarboximide (14): 2,1 l-bis (l-hexylheptyl ) benzo [13,14] pentapheno [3,4,5-IE / ": 10,9.8- 'e ⁇ diisoquinoline-l, 3,10,12 (2H, LLH) -tetraon (la, 100 mg, 0.114 mmol) was dissolved in pyrrolidine (40 mL), stirred at room temperature for 24 h, evaporated to dryness and purified by column chromatography (silica gel, chloroform) yield 73 mg (68%) of a green solid, mp> 250 ° C.
- Example 2 AvV-f) i- (1-hexylheptyl) -2,1,3-dipyrrolidinoterrorene-3,4: 11,12-tctracarboxylic acid bis-dicarboximide (15): 2,11 -bis (1 - hexylhcptyl) bcnzo [13.14] pentanothiopheno [3.4.5-def.
- IR (ATR): v 2952 (m), 2919 (s), 2850 (m), 2361 (w), 1691 (s), 1649 (s), 1583 (s), 1572 (s), 1505 (w ), 1456 (m), 1418 (w), 1350 (s), 1323 (s), 1302 (m), 1248 (m).
- Example 3 A v V -di (1-hexyheptyl) -2-pyrrolidinoquaterryl-3,4: 13,14-tetracarboxylic acid bis-dicarboximide (16): Quatcrrylene-3, 4: 1. 1,4-tetraearbonic acid 3.4: 1 3.
- R f sica gel, chloroform
- IR (ATR): v 2954.8 (m), 2924.9 (s), 2855.0 (m), 1688.7 (vs), 1650.3 (s), 1594.9 (m), 1568.6 (vs), 1542.3 (w), 1500.3 (w ), 1484.0 (w), 1457.4 (w), 1414.5 (w), 1391.1 (w), 1346.2 (vs), 1322.1 (m), 1287.6 (s), 1248.1 (w), 1230.1 (m), 1 174.2 ( w), 1 126.3 (w), 1105.6 (w), 1077.9 (w), 1052.0 (w), 946.4 (w), 908.5 (w), 840.0 (w), 807.8 (m), 751.9 (w), 732.0 (w), 668.6 cm -1 (w).
- Example 4 V, VI) i- (I -hexylhepty-1) -2,15-dipyrrolidinoquatricarbonyl-3,4: 13,14-tetracarboxylic acid bis-di-maleimide (17): quaterrylene-3,4: 1 14-tetracarboxylic acid 3.4: 1. 3. 14-bis (1-hexylheptylimide) (2a, 100 mg, 0.100 mmol) is dissolved in pyrrolidine (40 mL), stirred for 14 d at room temperature, evaporated to dryness and s 1 hrom ato rap hi sc h (silica gel, chloroform). Y.
- Example 5 Compounds 19/20: Compound 18 (H.Langhals et al., DE 102008061452; Chrn. Abstr. 2009, 151, 58174), (see Fig. 5, 100 mg, 0.114 mmol) was dissolved in pyrrolidine (40 mL ), stirred for 14 d at room temperature, evaporated to dryness and purified by column chromatography (silica gel, chloroform). Y. 74 mg (78%) of green solid, mp> 250 ° C. R f (silica gel, chloroform): 0.73.
- IR (ATR): v 3316.6 (w), 2951.9 (w), 2919.4 (m), 2852.1 (m), 1694.6 (m), 1669.6 (s), 1639.7 (m), 1622.8 (s), 1598.7 (s ), 1585.6 (vs), 1551.0 (s), 1529.6 (m).
- Dye solar cells Various Perylen-, Terrylen- or Quaterryleneducationen were with Help of Grätzel solar cells tested on their efficiency as a sensitizer for obtaining electrical energy from solar energy.
- the cells were irradiated with daylight in cloudy skies and a radiation intensity of 20,000 to 30,000 lux.
- Grätzel cells commercial nanostructured titanium dioxide coated plates from a manufacturing series were used.
- As a redox negative sequence system a standard electrolyte using iodine and iodide (iodine in alium iodide solution) was used. The operating point of highest power was determined by a successive approach. The thus determined performances of the cells with different sensitizers were normalized to the performance of the commercial sensitizer 23 (ruthenium complex), which is known for its efficiency and used in practice.
- Figure 2 Scheme for the synthesis of Quaterrylenbisimiden as starting materials for the preparation according to the invention erfmdungs connections on the example of 2a.
- FIG. 4 Stepwise substitution of the terrylene bisimide Ia and the quaterrylene bisimide
- FIG. 5 Substitution of imidazole operylene 18 with pyrrolidine for the preparation of compounds according to the invention.
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PCT/EP2013/074770 WO2014083011A2 (de) | 2012-11-27 | 2013-11-26 | Aminosubstituierte peri-arylenfarbstoffe |
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DE102016004396A1 (de) | 2016-04-07 | 2017-10-12 | Heinz Langhals | Stark fluoreszierende und solvatochrome Naphthalincarboximide mit Phenyl- und Naphthyl-Substituenten |
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DE102005021362A1 (de) * | 2005-05-04 | 2006-11-09 | Basf Ag | Terrylen- und Quaterrylenderivate |
DE102011018815A1 (de) * | 2011-04-27 | 2012-10-31 | Heinz Langhals | s-13-Terrylenbisimid und Terrylen-3,4:11,12-tetracarbonsäurebisanhydrid |
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DE4236885A1 (de) | 1992-10-31 | 1994-05-05 | Basf Ag | Quaterrylentetracarbonsäureimide |
DE19848555A1 (de) * | 1998-10-21 | 2000-04-27 | Heinz Langhals | Neue Fluoreszenzfarbstoffe durch Kern-Erweiterung von Perylen-3,4:9,10-tetracarbonsäurebisimiden |
DE102007004016A1 (de) * | 2007-01-26 | 2008-07-31 | Langhals, Heinz, Prof. Dr. | Bichromophore Perylenabkömmlinge für Solarenergiesysteme |
JP2008222605A (ja) * | 2007-03-09 | 2008-09-25 | Chisso Corp | 新規なペリレン誘導体およびそれを用いた光電変換素子 |
DE102008061452A1 (de) * | 2007-12-12 | 2010-07-08 | Langhals, Heinz, Prof. Dr. | Imidazoloperylenbisimide |
DE102007059683A1 (de) * | 2007-12-12 | 2009-06-18 | Langhals, Heinz, Prof. Dr. | Diazepinoperylene |
WO2011092028A1 (de) * | 2010-01-29 | 2011-08-04 | Ludwig-Maximilians-Universität München | Nanopartikel und nanotinte |
DE102011116207A1 (de) | 2011-10-14 | 2013-04-18 | Heinz Langhals | Perylenfarbstoffe mit zu den Carbonylgruppen benachbarten Amino-Gruppen |
DE102012002678A1 (de) | 2012-02-09 | 2013-08-14 | Heinz Langhals | Eine einstufige Synthese von Perylen-3,4-dicarbonsäureanhydrid |
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DE102005021362A1 (de) * | 2005-05-04 | 2006-11-09 | Basf Ag | Terrylen- und Quaterrylenderivate |
DE102011018815A1 (de) * | 2011-04-27 | 2012-10-31 | Heinz Langhals | s-13-Terrylenbisimid und Terrylen-3,4:11,12-tetracarbonsäurebisanhydrid |
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