EP3818035A1 - Molecular organic materials derived from anionic para-quinone methide dyes and the like, with special optical effects - Google Patents
Molecular organic materials derived from anionic para-quinone methide dyes and the like, with special optical effectsInfo
- Publication number
- EP3818035A1 EP3818035A1 EP19741981.5A EP19741981A EP3818035A1 EP 3818035 A1 EP3818035 A1 EP 3818035A1 EP 19741981 A EP19741981 A EP 19741981A EP 3818035 A1 EP3818035 A1 EP 3818035A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- group
- represent
- aryl
- 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.)
- Pending
Links
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 title description 98
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 title description 76
- 230000003287 optical effect Effects 0.000 title description 24
- 239000000975 dye Substances 0.000 title description 8
- 125000000129 anionic group Chemical group 0.000 title description 5
- 239000011368 organic material Substances 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 119
- 239000000049 pigment Substances 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 239000002932 luster Substances 0.000 claims abstract description 10
- 230000005693 optoelectronics Effects 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 294
- 125000001188 haloalkyl group Chemical group 0.000 claims description 106
- 125000005843 halogen group Chemical group 0.000 claims description 98
- 125000003118 aryl group Chemical group 0.000 claims description 94
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 93
- 125000000623 heterocyclic group Chemical group 0.000 claims description 61
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 59
- -1 OR26 Chemical compound 0.000 claims description 54
- 125000001072 heteroaryl group Chemical group 0.000 claims description 53
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 229910052702 rhenium Inorganic materials 0.000 claims description 12
- 229910052727 yttrium Inorganic materials 0.000 claims description 12
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 125000004434 sulfur atom Chemical group 0.000 claims description 8
- 150000001449 anionic compounds Chemical class 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910001412 inorganic anion Inorganic materials 0.000 claims description 7
- 150000002891 organic anions Chemical class 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 claims description 6
- 150000001767 cationic compounds Chemical class 0.000 claims description 6
- 229910001411 inorganic cation Inorganic materials 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 125000002619 bicyclic group Chemical group 0.000 claims description 5
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 5
- 229960001231 choline Drugs 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 5
- IHFXMTOFDQKABX-UHFFFAOYSA-N n-methylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCNC IHFXMTOFDQKABX-UHFFFAOYSA-N 0.000 claims description 5
- 150000002892 organic cations Chemical class 0.000 claims description 5
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 5
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 5
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 5
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 claims description 5
- SEACXNRNJAXIBM-UHFFFAOYSA-N triethyl(methyl)azanium Chemical compound CC[N+](C)(CC)CC SEACXNRNJAXIBM-UHFFFAOYSA-N 0.000 claims description 5
- ZNEOHLHCKGUAEB-UHFFFAOYSA-N trimethylphenylammonium Chemical compound C[N+](C)(C)C1=CC=CC=C1 ZNEOHLHCKGUAEB-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- ZJHQDSMOYNLVLX-UHFFFAOYSA-N diethyl(dimethyl)azanium Chemical compound CC[N+](C)(C)CC ZJHQDSMOYNLVLX-UHFFFAOYSA-N 0.000 claims description 4
- 125000001477 organic nitrogen group Chemical group 0.000 claims description 4
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 235000005822 corn Nutrition 0.000 claims description 3
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims description 2
- 240000008042 Zea mays Species 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 69
- 238000006243 chemical reaction Methods 0.000 description 61
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical group [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 46
- 229940031826 phenolate Drugs 0.000 description 46
- 238000000034 method Methods 0.000 description 36
- 239000002243 precursor Substances 0.000 description 30
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 29
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 26
- 239000003153 chemical reaction reagent Substances 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 23
- 150000004678 hydrides Chemical class 0.000 description 22
- 239000007800 oxidant agent Substances 0.000 description 22
- 230000001590 oxidative effect Effects 0.000 description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 21
- 239000010408 film Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 14
- 239000012965 benzophenone Substances 0.000 description 14
- 238000010511 deprotection reaction Methods 0.000 description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000006471 dimerization reaction Methods 0.000 description 9
- 239000000543 intermediate Substances 0.000 description 9
- 150000004053 quinones Chemical class 0.000 description 9
- DTQVDTLACAAQTR-UHFFFAOYSA-N trifluoroacetic acid Substances OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 230000001404 mediated effect Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000006069 Suzuki reaction reaction Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- CSRZQMIRAZTJOY-UHFFFAOYSA-N trimethylsilyl iodide Substances C[Si](C)(C)I CSRZQMIRAZTJOY-UHFFFAOYSA-N 0.000 description 5
- HBEDSQVIWPRPAY-UHFFFAOYSA-N 2,3-dihydrobenzofuran Chemical compound C1=CC=C2OCCC2=C1 HBEDSQVIWPRPAY-UHFFFAOYSA-N 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical group OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 4
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical class OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 150000003509 tertiary alcohols Chemical class 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 229910015845 BBr3 Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000004922 lacquer Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229960004011 methenamine Drugs 0.000 description 3
- 125000005525 methide group Chemical group 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- HRLDHROCDBYHAU-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3,5-ditert-butyl-4-hydroxyphenyl)methylidene]cyclohexa-2,5-dien-1-one Chemical group C1=C(C(C)(C)C)C(=O)C(C(C)(C)C)=CC1=CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 HRLDHROCDBYHAU-UHFFFAOYSA-N 0.000 description 2
- YFRVHGSNHTTWEK-UHFFFAOYSA-N 4-[(4-hydroxy-2,3,5,6-tetramethylphenyl)methyl]-2,3,5,6-tetramethylphenol Chemical compound CC1=C(O)C(C)=C(C)C(CC=2C(=C(C)C(O)=C(C)C=2C)C)=C1C YFRVHGSNHTTWEK-UHFFFAOYSA-N 0.000 description 2
- GWLULALJCBXHTF-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)methylidene]cyclohexa-2,5-dien-1-one Chemical compound C1=CC(O)=CC=C1C=C1C=CC(=O)C=C1 GWLULALJCBXHTF-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 241000209149 Zea Species 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000001204 arachidyl 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])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
- DIBHLCJAJIKHGB-UHFFFAOYSA-N dec-5-ene Chemical compound [CH2]CCCC=CCCCC DIBHLCJAJIKHGB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 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 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
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- 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 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000012649 demethylating agent Substances 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- BUMGIEFFCMBQDG-UHFFFAOYSA-N dichlorosilicon Chemical class Cl[Si]Cl BUMGIEFFCMBQDG-UHFFFAOYSA-N 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000000132 electrospray ionisation Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000001021 fluorone dye Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical compound [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 235000021384 green leafy vegetables Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005305 interferometry Methods 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 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
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- DZFWNZJKBJOGFQ-UHFFFAOYSA-N julolidine Chemical compound C1CCC2=CC=CC3=C2N1CCC3 DZFWNZJKBJOGFQ-UHFFFAOYSA-N 0.000 description 1
- CFHGBZLNZZVTAY-UHFFFAOYSA-N lawesson's reagent Chemical compound C1=CC(OC)=CC=C1P1(=S)SP(=S)(C=2C=CC(OC)=CC=2)S1 CFHGBZLNZZVTAY-UHFFFAOYSA-N 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001393 microlithography Methods 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- PHWISQNXPLXQRU-UHFFFAOYSA-N n,n-dimethylcarbamothioyl chloride Chemical compound CN(C)C(Cl)=S PHWISQNXPLXQRU-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000004770 neurodegeneration Effects 0.000 description 1
- 208000015122 neurodegenerative disease Diseases 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-M oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC([O-])=O ZQPPMHVWECSIRJ-KTKRTIGZSA-M 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- USPWKWBDZOARPV-UHFFFAOYSA-N pyrazolidine Chemical compound C1CNNC1 USPWKWBDZOARPV-UHFFFAOYSA-N 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 1
- 239000004984 smart glass Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- DGQOCLATAPFASR-UHFFFAOYSA-N tetrahydroxy-1,4-benzoquinone Chemical compound OC1=C(O)C(=O)C(O)=C(O)C1=O DGQOCLATAPFASR-UHFFFAOYSA-N 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- BRNULMACUQOKMR-UHFFFAOYSA-N thiomorpholine Chemical compound C1CSCCN1 BRNULMACUQOKMR-UHFFFAOYSA-N 0.000 description 1
- 238000007280 thionation reaction Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000005389 trialkylsiloxy group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000000169 tricyclic heterocycle group Chemical group 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/40—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by doubly-bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
- C07C225/02—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton
- C07C225/04—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated
- C07C225/08—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated and containing rings
- C07C225/12—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated and containing rings with doubly-bound oxygen atoms bound to carbon atoms being part of rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/703—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups
- C07C49/747—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/753—Unsaturated compounds containing a keto groups being part of a ring containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- 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
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/02—Diaryl- or thriarylmethane dyes derived from diarylmethanes
-
- 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
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/06—Hydroxy derivatives of triarylmethanes in which at least one OH group is bound to an aryl nucleus and their ethers or esters
-
- 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
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/14—Styryl dyes
- C09B23/148—Stilbene dyes containing the moiety -C6H5-CH=CH-C6H5
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
Definitions
- the present invention relates to sterically congested, V-shaped anionic /3 ⁇ 4/rc/-quinonc methide derivatives (more particularly 4-(4-hydroxybenzylidene)cyclohexa-2,5-dienone) and their thio counterparts (that encompasses compounds bearing an extra aryl motif on methylidene bridge position, comprised of only two main "electroactive arms” so that their overall key V-shaped topology is preserved), as well as their use as molecular chromophores of interest as such (e.g. dye molecules) and as components of pigments displaying special optical effects or of organic metal- like liquid films.
- V-shaped anionic /3 ⁇ 4/rc/-quinonc methide derivatives more particularly 4-(4-hydroxybenzylidene)cyclohexa-2,5-dienone
- their thio counterparts that encompasses compounds bearing an extra aryl motif on methylidene bridge position, comprised of only two main "electroactive
- said anionic /3 ⁇ 4/rc/-(thio)quinonc methide derivatives of tunable electronic features can serve as the building blocks of organized organic molecular materials exhibiting special optical properties including (1) metal-like reflection or (2) iridescence or pearl-luster effects, that are referred to as special optical effects that respectively originate from interaction of light with the material surface, in the former case (1), or with the bulk material, in the latter case (2).
- Special effect pigments are nano- or meso-particulate materials that give additional color effects, such as angular color dependence (iridescence, luster) or texture.
- luster pigments these pigments are subdivided in 2 classes: metal effect pigments and pearl luster pigments (see [Special Effect Pigments, G. Pfaff, 2008, 2 nd Rev. ed., Vincentz Network GmbH & Co. KG, Hannover/Germany] and [Metal Effect Pigments, Fundamentals and Applications, P. Willing, 2006, Vincentz Network GmbH & Co. KG, Hannover/Germany]).
- effect pigments based on organic structures, amongst which so-called “photonic crystals” mostly encountered in Nature (e.g. guanine platelets isolated from fish scales and certain liquid crystals), the industry of“effect pigments” relies almost exclusively on metallic particles and purposely-structured inorganic materials (e.g.
- crystalline HgCf platelets lead, arsenic or bismuth salts, platelet-shaped PbHPO i, mica- T1O2 combination, basic lead carbonate, bismuth oxychloride, aluminum platelets coated with Fe203, metal oxide-coated synthetic mica, iron oxides mica, chromium(III) oxide mica, AI2O3 flakes, S1O2 flakes, borosilicate flakes).
- metal effect pigment is a subfamily of the“metallic pigment” group that includes“metal pigments” (consisting of pure metals or metal alloys) and either inorganic or organic color pigments possessing at least one metal atom in their formula.
- metal pigments consisting of pure metals or metal alloys
- inorganic or organic color pigments possessing at least one metal atom in their formula.
- the present invention relies on the self-assembly of specifically-conceived chromophores that feature huge molar extinction coefficients and very sharp absorption bands.
- Liquid mirror may be shaped by rotation or by thermal or magnetic fields (see [Truong, L. et al. Appl. Opt., 2005, 44, 1595], [Dery et al. Chem. Mater., 2008, 20, 6420-6426] and [EP1361585]), or may enter in the composition of a reflective renewable fluid in a device submitted to highly damaging, extremely intense photon beams [US 20020135908]
- the chromophoric nature of the molecules that originates in a particularly efficient inner charge transfer (characterized by both a high molar extinction coefficient and a sharp absorption band) induce the self-assembly of films or layered surfaces displaying highly reflective properties without resort to any metal, paving the way to inexpensive, environmentally benign and durable liquid mirrors (moreover possibly electroswitchable, given the reducible character of the carbenium here described).
- the present invention relates thus to a compound of the following formula (I):
- ⁇ X represents an oxygen or a sulfur atom
- ⁇ Ro represents a hydrogen atom, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, aryl-(Ci- C 6 )alkyl, heteroaryl-(Ci-C 6 )alkyl, cycloalkyl, cycloalkyl-(Ci-C 6 )alkyl, heterocycle, heterocycle-(Ci-C 6 )alkyl, OR5, SR6, NR7R8, PR9R 10 , CORn, CO 2 R 12 , CONR 13 R 14 , SO 2 R 15 ,
- Z represents C or N + A z and Z’ represents N or N + -R c ’ A z , wherein
- a z represents a monovalent organic or inorganic anion
- R a and R e each represent, independently of each other, a hydrogen atom, a halogen atom, a (Ci-C2o)alkyl, (Ci-C2o)haloalkyl, aryl, heteroaryl, aryl-(Ci-C 6 )alkyl, heteroaryl- (Ci-C 6 )alkyl, cycloalkyl, cycloalkyl-(Ci-C 6 )alkyl, heterocycle, heterocycle-(Ci-C 6 )alkyl, OR 22 or SR 23 group, and
- R b , R c and R d each represent, independently of each other, a hydrogen atom, a halogen atom or a (Ci-C2o)alkyl, (Ci-C2o)haloalkyl, cycloalkyl, cycloalkyl-(Ci-C 6 )alkyl, heterocycle, heterocycle-(Ci-C 6 )alkyl, 0(Ci-C 2 o)alkyl group;
- C 2 o)haloalkyl aryl, heteroaryl, aryl-(Ci-C 6 )alkyl, heteroaryl-(Ci-C 6 )alkyl, cycloalkyl, cycloalkyl-(Ci-C 6 )alkyl, heterocycle, heterocycle-(Ci-C 6 )alkyl, (CH 2 ) m OR 24 , (CH 2 ) m SR 25 , OR26, SR27, NR28R29, PR30R31, COR32, CO2R33, CONR34R35, OCOR36, OCO2R37,
- NR 38 COR 39 or NR 40 SO 2 R 41 group, wherein m and m’ are, independently of each other, equal to 1, 2 or 3, preferably 1;
- C 2 o)haloalkyl aryl, heteroaryl, aryl-(Ci-C 6 )alkyl, heteroaryl-(Ci-C 6 )alkyl, cycloalkyl, cycloalkyl-(Ci-C 6 )alkyl, heterocycle, heterocycle-(Ci-C 6 )alkyl, (CH 2 ) m OR 24 , (CH 2 ) m SR 25 , OR26, SR27, NR28R29, PR30R31, COR32, CO2R33, CONR34R35, OCOR36, OCO2R37,
- NR 38 COR 39 or NR 40 SO 2 R 41 group, wherein m and m’ are, independently of each other, equal to 1, 2 or 3, preferably 1;
- R4 groups form together a bond or a chain selected from the group consisting of -C(R4 2 R43)-, -(CH 2 ) lake-, -Si(R4 4 R45)-, -(CH 2 ) p -Y-(CH 2 )q-, and -Y-(CR46R4 7 )r-Y’-, wherein:
- Y and Y’ each represent, independently of each other, O, S or NI ,
- n 2 or 3
- p is equal to 1 or 2
- q is equal to 0 or 1 ,
- R4 2 andR43 each represent, independently of each other, a (Ci-C 6 )alkyl or an aryl group
- R 44 and R 45 each represent, independently of each other, a (Ci-C 6 )alkyl or an aryl group
- R 46, R 47 and R68 each represent, independently of each other, a hydrogen atom, a
- Lx represents a bond, or a group selected from the group consisting of:
- R 3 ⁇ 4 Ri, R m , R n , R o , R P , R q and R r each represent, independently of each other, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, aryl, heteroaryl, aryl-(Ci-C 6 )alkyl, heteroaryl-(Ci-C 6 )alkyl, cycloalkyl, cycloalkyl-(Ci-C 6 )alkyl, heterocycle, heterocycle-(Ci-C6)alkyl, OR 48 , SR 49 , NR50R5 1 , COR 52 , C0 2 R 53 or CONR5 4 R55 group ; and
- R 2 and R3 each represent, independently of each other, a hydrogen atom, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (Ci-C 6 )haloalkyl, aryl, heteroaryl, aryl-(Ci-C 6 )alkyl, heteroaryl-(Ci-C 6 )alkyl, cycloalkyl, cycloalkyl-(Ci-C 6 )alkyl, heterocycle, heterocycle-(Ci-C6)alkyl, OR56, SR57, NR58R59, COR60, C0 2 R6i or CONR6 2 R63 group ;
- R f and R 2 , and R g and R 3 form together with the carbon atoms that carry them a cycloalkenyl or aryl group, wherein R k and Ri are as defined above;
- R5, R6, R 48 , R 49 , R56 and R57 are not H;
- R 22 to R 23 and R 26 to R 27 each represent, independently of each other a (Ci-C2o)alkyl, (Ci-C2o)haloalkyl, aryl, heteroaryl, aryl-(Ci-C6)alkyl, heteroaryl-(Ci-C6)alkyl, cycloalkyl, cycloalkyl-(Ci-C6)alkyl, heterocycle or heterocycle-(Ci-C6)alkyl group, preferably a (Ci-C2o)alkyl, notably (Ci-C6)alkyl group, said group being optionally substituted by one or more groups selected from a halogen atom, a (Ci-C6)alkyl, (Ci-C6)haloalkyl, OR M , SR 65 and NR66R67 group, wherein R64 to R67 each represent, independently of each other, a hydrogen atom or a (Ci-C6)alkyl group;
- ⁇ Ro represents a hydrogen atom, a halogen atom, a (Ci-C6)alkyl, (Ci-C6)haloalkyl, aryl-(Ci-C6)alkyl, heteroaryl-(Ci-C6)alkyl, cycloalkyl, cycloalkyl-(Ci-C6)alkyl, heterocycle, heterocycle-(Ci-C 6 )alkyl, OR 5 , SR 6 , NR 7 R 8 , CORn, CO 2 R 12 , CONR 13 R 14 , SO 2 R 15 , CN or NO 2 group, or is selected from the group consisting of:
- Z represents C or N + A z and Z’ represents N or N + -R c ’ A z , wherein
- R a and R e each represent, independently of each other, a hydrogen atom, a halogen atom, a (Ci-C 2 o)alkyl, (Ci-C 2 o)haloalkyl, aryl, heteroaryl, aryl-(Ci-C 6 )alkyl, cycloalkyl, heterocycle, heterocycle-(Ci-C 6 )alkyl, OR 22 or SR 23 group, and
- ⁇ Ri represents a halogen atom, a (Ci-C 2 o)alkyl, (C 2 -C 6 )alkynyl, (Ci-C 2 o)haloalkyl, aryl, heteroaryl, aryl-(Ci-C 6 )alkyl, heteroaryl-(Ci-C 6 )alkyl, cycloalkyl, cycloalkyl-(Ci-C 6 )alkyl, heterocycle, heterocycle-(Ci-C 6 )alkyl, (CH2) m OR24, (CH 2 ) m SR25, OR 26 , SR 27 , NR 28 R 29 , COR 32 , OCOR 36 or NR 38 COR 39 group, wherein m and m’ are, independently of each other, equal to 1, 2 or 3, preferably 1;
- both R 4 groups form together a bond or a chain selected from the group consisting of -C(R 42 R 43 )-, -(CH 2 ) lake-, -Si(R 44 R 45 )-, -CH 2 -Y-CH 2 -, and -Y-CH 2 -CH 2 -Y’-, wherein:
- Y and Y’ each represent, independently of each other, O, S or NH,
- n 2 or 3
- R 42 andR 43 each represent, independently of each other, a (Ci-C 6 )alkyl or an aryl group, and
- R 44 and R 45 each represent, independently of each other, a (Ci-C 6 )alkyl or an aryl group;
- ⁇ Lx represents a bond, or a group selected from the group consisting of:
- R2 and R3 each represent, independently of each other, a hydrogen atom, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, (C 2 -Cr,)alkcnyl, (C 2 -Cr,)alkynyl, aryl, heteroaryl, cycloalkyl, heterocycle, OR 56 , SR57 or NR58R59 group ;
- R5 to R8, R11 to R15, R24, R25, R28, R29, R32, R36, R38, R39, R48 to R51, and R56 to R59 each represent, independently of each other, a hydrogen atom, a (Ci-C6)alkyl, (Ci-C6)haloalkyl, aryl, heteroaryl, aryl-(Ci-C6)alkyl, heteroaryl-(Ci-C6)alkyl, cycloalkyl, cycloalkyl-(Ci-C6)alkyl, heterocycle or heterocycle-(Ci-C6)alkyl group, preferably a hydrogen atom or a (Ci-C6)alkyl group, said group being optionally substituted by one or more groups selected from a halogen atom, a (Ci-C6)alkyl, (Ci-C6)haloalkyl, OR M , S FG and NR 66 R 67 group, wherein R 64 to R 67
- R 22 to R 23 and R 26 to R 27 each represent, independently of each other a (Ci-C 2 o)alkyl
- (Ci-C 6 )alkyl refers to a saturated, linear or branched hydrocarbon chain comprising from 1 to 6 carbon atoms, including, but not limited to, methyl, ethyl, «-propyl, isopropyl, «-butyl, isobutyl, .vec- butyl, tert- butyl, «-pentyl, «-hexyl and the like.
- (Ci-C2o)alkyl refers to a saturated, linear or branched hydrocarbon chain comprising from 1 to 20 carbon atoms, including, but not limited to, the (Ci-C 6 )alkyl groups enumerated above, and octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and the like.
- (C2-C6)alkenyl refers to a linear or branched hydrocarbon chain comprising at least one double bond and comprising from 2 to 6 carbon atoms including, but not limited to, ethenyl (e.g. vinyl), propenyl (e.g. allyl) and the like.
- (C2-C6)alkynyl refers to a linear or branched hydrocarbon chain comprising at least one triple bond and comprising from 2 to 6 carbon atoms including, but not limited to, ethynyl, propynyl and the like.
- cycloalkyl refers to a saturated hydrocarbon ring comprising from 3 to 7, advantageously from 5 to 7, carbon atoms including, but not limited to, cyclohexyl, cyclopentyl, cyclopropyl, cycloheptyl and the like.
- cycloalkenyl refers to an unsaturated hydrocarbon ring comprising from 3 to 7, advantageously from 5 to 6, carbon atoms, including, but not limited to, cyclopentenyl, cyclohexenyl, cyclopentadienyl, cyclohexadienyl and the like.
- a saturated heterocycle is more particularly a 3-, 4-, 5- or 6-membered, even more particularly a 5- or 6-membered saturated monocyclic heterocycle such as an aziridine, an azetidine, a pyrrolidine, a tetrahydrofuran, a l,3-dioxolane, a tetrahydrothiophene, a thiazolidine, an isothiazolidine, an oxazolidine, an isoxazolidine, an imidazolidine, a pyrazolidine, a triazolidine, a piperidine, a piperazine, a l,4-dioxane, a morpholine or a thiomorpholine.
- An unsaturated heterocycle is more particularly an unsaturated monocyclic or bicyclic heterocycle, each cycle comprising 5 or 6 members, such as 1 7-azirinc, a pyrroline, a dihydrofuran, a l,3-dioxolene, a dihydrothiophene, a thiazoline, an isothiazoline, an oxazoline, an isoxazoline, an imidazoline, a pyrazoline, a triazoline, a dihydropyridine, a tetrahydropyridine, a dihydropyrimidine, a tetrahydropyrimidine, a dihydropyridazine, a tetrahydropyridazine, a dihydropyrazine, a tetrahydropyrazine, a dihydrotriazine, a tetrahydrotriazine, a l,4-dioxen
- 2,3-dihydrobenzofuran (coumaran), a 2,3-dihydrobenzothiophene, a l,3-benzodioxole, a 1,3- benzoxathiole, a benzoxazoline, a benzothiazoline, a benzimidazoline, a chromane or a chromene.
- aryl refers to an aromatic hydrocarbon group comprising preferably 6 to 14 carbon atoms and comprising one or more fused rings, such as, for example, a phenyl, naphthyl or anthracenyl group.
- fused rings such as, for example, a phenyl, naphthyl or anthracenyl group.
- it will be a phenyl group.
- heteroaryl refers to an aromatic heterocycle as defined above. It can be more particularly an aromatic monocyclic, bicyclic or tricyclic heterocycle, each cycle comprising 5 or 6 members, such as a pyrrole, a furan, a thiophene, a thiazole, an isothiazole, an oxazole, an isoxazole, an imidazole, a pyrazole, a triazole, a pyridine, a pyrimidine, an indole, a benzofuran, a benzothiophene, a benzothiazole, a benzoxazole, a benzimidazole, an indazole, a benzotriazole, a quinoline, an isoquinoline, a cinnoline, a quinazoline, a quinoxaline, a carbazole, or a julolidine.
- cycloalkyl-(Ci-C 6 )alkyl refers to any cycloalkyl group as defined above, which is bound to the molecule by means of a
- heterocycle-(Ci-C 6 )alkyl refers to a heterocycle group as defined above, which is bound to the molecule by means of a
- aryl-(Ci-C 6 )-alkyl refers to any aryl group as defined above, which is bound to the molecule by means of a (Ci-C 6 )-alkyl group as defined above. In particular, it can be a benzyl group.
- heteroaryl-(Ci-C 6 )alkyl refers to a heteroaryl group as defined above, which is bound to the molecule by means of a
- organic or inorganic anion refers, within the sense of the present invention, to a negatively-charged counter-ion. It can be in particular a halide (fluoride, chloride, bromide, iodide), perchlorate, nitrate, sulfate, alkylsulfate, benzenesulfonate, / ⁇ -toluene sulfonate, chlorosulfonate, fluorosulfonate, trifluorosulfonate, methanesulfonate, benzenesulfinate, tetrafluoroborate, acetate, trifluoroacetate, propionate, benzoate, oxalate, succinate, oleate, stearate, citrate, hydrogenophosphate, dihydrogenophosphate or hexafluorophosphate anion.
- it is a hexafluorophosphate, tetrafluoroborate
- organic or inorganic cation refers, within the sense of the present invention, to a positively-charged counter-ion. It can be in particular an ammonium or a phosphonium ion or the conjugate acid of an organic nitrogen-containing bicyclic base.
- ammonium refers to any cation of the following formula N(R’R”R”’R””) + , wherein R’, R”, R’” and R””, each represent, independently of each other, an optionally substituted (Ci-C2o)alkyl, notably (Ci-C 6 )alkyl, aryl or aryl-(Ci-C 6 )-alkyl group, said group being as defined above.
- It can be in particular a tetrabutylammonium, a tetrapropylammonium, a tetraethylammonium, a tetramethylammonium, a benzyltrimethylammonium, a phenyltrimethylammonium, a hexadecylmethylammonium a triethylmethylammonium or a diethyldimethylammonium cation, or a choline.
- phosphonium refers to any cation of the following formula P(R’R”R”’R””) + , wherein R’, R”, R’” and R”” are as defined above.
- R’, R”, R’” and R” each represent, independently of each other, a (Ci-C 6 )alkyl or aryl group. It can be notably a tetrabutylphosphonium or a tetraphenylphosphonium cation.
- organic nitrogen-containing bicyclic base refers to a saturated or unsaturated, aromatic or non-aromatic bicycle, consisting in two fused, bridged or spiro rings, preferably fused or bridged rings, advantageously comprising 3 to 10, notably 4 to 8 atoms in each ring, in which the atoms of the ring(s) comprise one or more, advantageously 1 to 3, nitrogen atom(s), the remainder being carbon atoms ft can be notably l,5-Diazabicyclo[4.3.0]non-5-ene (DBN), l,8-Diazabicyclo[5.4.0]undec-7-ene (DBU), l,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) or l,4-Diazabicyclo[2.2.2]octane (DABCO).
- X represents an oxygen atom
- Ro represents a hydrogen atom, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, aryl-(Ci-C 6 )alkyl, heteroaryl-(Ci-C 6 )alkyl, cycloalkyl, cycloalkyl-(Ci-C 6 )alkyl, heterocycle, heterocycle-(Ci-C 6 )alkyl, ORs, SR 6 , NR 7 R 8 , CN or NO2 group, or is selected from the group consisting of:
- Z represents C or N + A z and Z’ represents N or N + -R c ’ A z , wherein
- a z represents a monovalent organic or inorganic anion
- R c ’ represents a (Ci-C 6 )alkyl group
- R a and R e each represent, independently of each other, a hydrogen atom, a halogen atom, a (Ci-C2o)alkyl, (Ci-C2o)haloalkyl, aryl, heteroaryl, cycloalkyl, heterocycle, OR22 or SR 23 group, and
- R b , R c and R d each represent, independently of each other, a hydrogen atom, a halogen atom or a (Ci-C2o)alkyl, (Ci-C2o)haloalkyl, cycloalkyl, heterocycle or 0(Ci-C 2 o)alkyl group.
- Ro represents a hydrogen atom, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, such as CF 3 , cycloalkyl, heterocycle, OR 5 , SR 6 , NR 7 R 8 , CN or NO2 group, or is selected from the group consisting of:
- a z represents a monovalent organic or inorganic anion
- R a and R e each represent, independently of each other a hydrogen atom, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, OR 22 or SR 23 group, and
- R b , R c and R d each represent, independently of each other, a hydrogen atom, a halogen atom or a 0(Ci-C 2 o)alkyl, (Ci-C 6 )alkyl or (Ci-C 6 )haloalkyl group.
- Ro represents a hydrogen atom, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, such as CF 3 , cycloalkyl, heterocycle, OR 5 , SR 6 , NR7R8, CN or NO2 group, or is:
- R b , R c and R d each represent, independently of each other, a hydrogen atom, a halogen atom or a 0(Ci-C 2 o)alkyl, (Ci-C 6 )alkyl or (Ci-C 6 )haloalkyl group.
- Ro represents a hydrogen atom, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, such as CF 3 , OR 5 , NR 7 R 8 , CN or NO2 group, or
- R a and R e each represent, independently of each other, a hydrogen atom, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl or OR22 group, and
- R b , R c and R d each represent a 0(Ci-C 2 o)alkyl group or a hydrogen atom.
- R a and R e are preferably the same.
- R b , R c and R d are preferably the same.
- Ro represents a hydrogen atom, a (Ci-C 6 )alkyl, OR 5 , NR 7 R 8 , or a CN group, notably a hydrogen atom, NR 7 R 8 , or a CN group, advantageously a hydrogen atom.
- R4 represents a halogen atom, a (Ci-C 2 o)alkyl, notably (Ci-C6)alkyl, (Ci-C 2 o)haloalkyl, notably (Ci-C6)haloalkyl, aryl, heteroaryl, cycloalkyl, heterocycle, (CH 2 ) m OR 24 , (CH 2 ) m SR 25 , OR 26 , SR 27 or NR 28 R 2 9 group, wherein m and m’ are, independently of each other, equal to 1, 2 or 3, preferably 1 ;
- both R4 groups form together a bond or a chain selected from the group consisting of -C(R4 2 R43)-, -(CH 2 ) n -, -Si(R44R4 5 )- and -Y-CH 2 -CH 2 -Y’-, wherein:
- R42 and R43 each represent, independently of each other, a (Ci-C 6 )alkyl or an aryl group, preferably a (Ci-C 6 )alkyl group, and
- both R4 groups form together a bond or a chain selected from the group consisting of - C(R4 2 R43)-, ( CFt 2 ) n - , -Si(R4 4 R45)- and -Y-CH 2 -CH 2 -Y’-, wherein:
- n 2 or 3
- R 42 andR 43 each represent, independently of each other, a (Ci-C 6 )alkyl group
- R 44 and R 45 each represent, independently of each other, a (Ci-C 6 )alkyl group.
- R4 groups form together a bond or a chain selected from the group consisting of - C(R 42 R 43 )-, -CH2-CH2- , -Si(R4 4 R4 5 )- and -O-CH2-CH2-O-, wherein R 42 to R 45 , each represent, independently of each other, a (Ci-C 6 )alkyl group.
- R4 represents a halogen atom, a (Ci-C2o)alkyl, notably (Ci-C 6 )alkyl, (Ci-C2o)haloalkyl, notably (Ci-C 6 )haloalkyl, aryl, heteroaryl, cycloalkyl, heterocycle, (CH 2 ) m OR 24 , (CH 2 ) m SR 25 , OR 26 , SR 27 or NR 28 R 29 group, wherein m and m’ are, independently of each other, equal to 1, 2 or 3, preferably 1.
- R4 represents a halogen atom, a (Ci-C6)alkyl, (Ci-C6)haloalkyl, aryl, (CH 2 ) m OR 24 , (CH 2 ) m SR 25 , OR 26 , SR 27 or NR 28 R 29 , group, wherein m and m’ are, independently of each other, equal to 1, 2 or 3, preferably 1.
- R4 represents a halogen atom, a (Ci-C6)alkyl, (Ci-C6)haloalkyl, aryl, CH 2 -OR 24 or OR 26 group, preferably a (Ci-C6)alkyl, aryl, CH 2 -OR 24 or OR 26 group, notably a (Ci-C6)alkyl group.
- Ri and R4 are the same, and are as defined in any of the above embodiments.
- R k , Ri, R m , R n , R o , R P , R q and R r each represent, independently of each other, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, aryl, heteroaryl, cycloalkyl, heterocycle, OR 48 , SR 49 or NR50R51 group ;
- R2 and R3 each represent, independently of each other, a hydrogen atom, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, aryl, heteroaryl, cycloalkyl, heterocycle, OR 56 , SR 57 or NR 58 R 59 group ;
- R f and R 2 , and R g and R 3 form together with the carbon atoms that carry them a cycloalkenyl or aryl group, wherein R k and Ri are as defined above.
- Lx represents a bond, or a group selected from the group consisting of:
- R k , Ri, R m , R n , R o , R P , R q and R r each represent, independently of each other, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, aryl, heteroaryl, cycloalkyl, heterocycle, OR 48 , SR 49 or NR50R51 group ;
- R2 and R3 each represent, independently of each other, a hydrogen atom, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, aryl, heteroaryl, cycloalkyl, heterocycle, OR 56 , SR 57 or NR 58 R 59 group ;
- Lx represents a bond, or a group selected from the group consisting of:
- R k , Ri, R m , R n , R o , R P , R q and R r each represent, independently of each other, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, such as CF 3 , aryl, heteroaryl, cycloalkyl or heterocycle group ;
- R 2 and R 3 each represent, independently of each other, a hydrogen atom, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, such as CF 3 , aryl, heteroaryl, cycloalkyl, heterocycle, OR 56 , SR 57 , or NR58R 59 group ;
- R 2 and R 3 both represent a hydrogen atom.
- Lx represents a bond, or a group selected from the group consisting of:
- R k , Ri, R m , R n , R o , R P , R q and R r each represent, independently of each other, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, such as CF 3 or aryl group ;
- R 2 and R 3 are the same.
- R k and Ri are the same, R m and R n are the same, R o and R p are the same, and R q and R r are the same.
- Lx represents a bond and R2 and R3 each represent, independently of each other, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, such as CF3, aryl, heteroaryl, cycloalkyl, heterocycle, OR 56 , SR 57 or NR 58 R 59 group;
- Lx represents a bond and R2 and R3 each represent, independently of each other, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, such as CF 3 , aryl, heteroaryl, OR 56 , SR 57 or NIL* Regroup ;
- R and Ri each represent, independently of each other, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, an aryl or a heteroaryl group, and R2 and R3 both represent a hydrogen atom.
- Lx represents a bond and R2 and R3 each represent, independently of each other, a halogen atom, a (Ci-C 6 )alkyl, aryl or OR 56 group ; or Lx represents , wherein R k and Ri, each represent, independently of each other, a halogen atom, a (Ci-C 6 )alkyl or aryl group, and R2 and R3 both represent a hydrogen atom.
- Lx represents a bond and R2 and R3 each represent, independently of each other, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, aryl, heteroaryl, cycloalkyl, heterocycle, OR 56 , SR 57 or NR 58 R 59 group, notably a halogen atom, a (Ci-C 6 )alkyl, (Ci-C6)haloalkyl, such as CF 3 , aryl, heteroaryl, OR 56 , SR 57 or NR 58 R 59 group, in particular a halogen atom, a (Ci-C6)alkyl, aryl or OR 56 group.
- R2 and R3 are the same.
- R 5 to Rg, R11 to R1 5 , R24, R2 5 , R28, R29, R 32, R 36, R 38 , R 39, R48 to R 51 , and R 5 6 to R 59 each represent, independently of each other, a hydrogen atom, a (Ci-C6)alkyl, (Ci-C6)haloalkyl, aryl, heteroaryl, aryl-(Ci-C6)alkyl, heteroaryl-(Ci-C6)alkyl, cycloalkyl, cycloalkyl-(Ci-C6)alkyl, heterocycle or heterocycle-(Ci-C6)alkyl group, preferably a hydrogen atom or a (Ci-C6)alkyl group, said group being optionally substituted by one or more groups selected from a halogen atom, a (Ci-C6)alkyl, (Ci-C6)haloalkyl, OR M , SR 65 and NR 66 R 67 group
- R 5 to Rg, R11 to R1 5 , R24, R2 5 , R28, R29, R 32, R 36, R 38 , R 39, R48 to R 51 , and R 56 to R 59 each represent, independently of each other, a (Ci-C6)alkyl group;
- R 22 to R 23 and R 26 to R 27 each represent, independently of each other a (Ci-C 2 o)alkyl, notably (Ci-C 6 )alkyl, (Ci-C 2 o)haloalkyl, notably (Ci-C 2 o)haloalkyl, aryl, heteroaryl, aryl-(Ci-C 6 )alkyl, heteroaryl-(Ci-C 6 )alkyl, cycloalkyl, cycloalkyl-(Ci-C 6 )alkyl, heterocycle or heterocycle- (Ci- Ce)alkyl group, preferably a (Ci-C 2 o)alkyl, notably (Ci-C 6 )alkyl group, said group being optionally substituted by one or more groups selected from a halogen atom, a (Ci-C 6 )alkyl, (Ci-C6)haloalkyl, OR 64 , SR 65 and NR 66
- R 22 to R 23 and R 26 to R 27 each represent, independently of each other a (Ci-C 2 o)alkyl, notably (Ci-C 6 )alkyl group.
- the invention relates to a compound of formula (I), wherein:
- ⁇ Ro represents a hydrogen atom, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, such as CF 3 , cycloalkyl, heterocycle, OR 5 , SR 6 , NR 7 R 8 , CN or NCk group, or is:
- R a and R e are the same and represent a hydrogen atom, a halogen atom, a (Ci-C2o)alkyl, notably (Ci-C 6 )alkyl, (Ci-C2o)haloalkyl, notably (Ci-C 6 )haloalkyl, OR 22 or SR 23 group, and
- R b , R c and R d each represent, independently of each other, a hydrogen atom, a halogen atom or a (Ci-C 6 )alkyl or a 0(Ci-C 2 o)alkyl group, preferably R b , R c and R d are the same; Ri and R4 are the same, and represent a halogen atom, a (Ci-C2o)alkyl, notably (Ci- C 6 )alkyl, (Ci-C2o)haloalkyl, notably (Ci-C 6 )haloalkyl, aryl, heteroaryl, cycloalkyl, heterocycle, (CH 2 ) m OR 24 , (CH 2 ) m SR 25 , OR 26 , SR 27 or NR 28 R 29 group, wherein m and m’ are, independently of each other, equal to 1, 2 or 3, preferably 1 ; and
- Lx represents a bond, or a group selected from the group consisting of:
- R2 and R3 are the same and represent a hydrogen atom, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, aryl, heteroaryl, cycloalkyl, heterocycle, OR 56 , SR 57 or NILxILy group ; with the proviso that:
- ⁇ X represents an oxygen atom
- ⁇ Ro represents a hydrogen atom, a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, such as CF3, OR5, NR7R8, CN or NO 2 group, or is: , wherein:
- R b , R c and R d each represent a hydrogen atom or a 0(Ci-C 2 o)alkyl group, preferably R b , R c and Rd are the same;
- Ri and R4 are the same, and represent a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, aryl, (CH 2 ) m OR 24 , (CFb) m’ SR 25 , OR 26 , SR 27 or NR 28 R 29 , group, wherein m and m’ are, independently of each other, equal to 1, 2 or 3, preferably 1 ; and
- Lx represents a bond and R 2 and R 3 are the same and represent a halogen atom, a (Ci- C 6 )alkyl, (Ci-C 6 )haloalkyl, such as CF 3 , aryl, heteroaryl, cycloalkyl, heterocycle, OR 56 ,
- the invention relates to a compound of formula (I), wherein:
- ⁇ Ro represents a hydrogen atom, a (Ci-C 6 )alkyl, OR 5 , NR 7 R 8 or a CN group, notably a hydrogen atom, NR7R8 or a CN group, advantageously a hydrogen atom;
- ⁇ Lx represents a bond
- ⁇ R2 and R3 are the same and represent a halogen atom, a (Ci-C 6 )alkyl, (Ci-C 6 )haloalkyl, such as CF3, aryl, heteroaryl, OR56, SR57 or NR58R59 group, in particular a halogen atom, a (Ci-C 6 )alkyl, aryl or OR56 group.
- R51, and R56 to R59 are as defined above.
- R5 to Rx, R11 to R15, R24, R25, R28, R29, R32, R36, R38, R39, R48 to R51, and R56 to R59 each represent, independently of each other, a (Ci-C 6 )alkyl group; and R22 to R23 and R26 to R27 each represent, independently of each other a (Ci-C2o)alkyl, notably (Ci-C 6 )alkyl group.
- a compound of the present invention is chosen among the following compounds:
- a compound of the present invention is chosen among compounds 1 to 6, 8 to 10. 13, 23. 24. 32 and 34 , in particular among compounds 1, 2 and 8.
- a compound of the present invention is compound 8.
- a + represents a monovalent, organic or inorganic cation.
- a + represents an ammonium or a phosphonium ion or the conjugate acid of an organic nitrogen-containing bicyclic base.
- a + is selected from the group consisting of tetrabutylammonium, tetrapropylammonium, tetraethylammonium, tetramethylammonium, benzyltrimethylammonium, phenyltrimethylammonium, hexadecylmethylammonium choline, triethylmethylammonium, diethyldimethylammonium, tetrabutylphosphonium, tetraphenylphosphonium, DBN-H + , DBU-H + , TBD-H + and DABCO-H + , preferably from the group consisting of tetrabutylammonium, tetrapropylammonium, tetraethylammonium, tetramethylammonium, benzyltrimethylammonium, phenyltrimethylammonium, hexadecylmethylammonium choline, triethyl
- the invention also relates to the use of a compound according to the invention as a chromophore.
- chromophore here refers to a molecule whose electronic absorption is at least situated in the spectral range of visible light (between ca. 400 nm and 700 nm), which is not exclusive of absorption in the near-UV and near-infrared domains.
- molecular chromophores possible applications span from bioimaging purposes, notably as a dye to stain cells, tissues or fibrillar structures like those associated with a variety of neurodegenerative diseases, among which Alzheimer’s disease, to the conception of new high-performance optical limiter devices relying on non-linear optical properties displayed by compounds objects of the invention.
- the invention also relates to a material comprising at least one compound according to the invention.
- the compounds according to the invention tend to self-assemble and form supramolecular materials.
- Said materials can be in the form of crystals, thin films, flakes, platelets or layers and other forms of low- dimensional materials (interfacial films) that may result from self-assembly of chromophores.
- Said supramolecular materials can be a pigment, advantageously a pigment of interest for its special optical effect(s).
- the invention relates to the use of the compounds (or said supramolecular materials) according to the invention as a pigment or dye.
- the invention also relates to a metal-like particle that comprises at least one compound according to the invention.
- Said particle might be embedded within a matrix, including but not limited to polymers, plastics, coating or cosmetic formulation, glass, ceramics, enamels.
- the invention also relates to a reflective, photonic, nanophotonic or optoelectronic device, that comprises at least one compound according to the invention.
- a reflective device can notably be a solid or liquid mirror.
- mirror refers to a reflective surface and includes, but is not limited to, a large mirror (e.g. for astronomy or LIDAR technologies), a smart mirror (displaying one or several of the following features: flexibility, transportability, switchability) or an organic-based metal- like liquid film.
- organic-based metal-like liquid film or OMELLF here refers to an organic molecule able to self-assemble to display a reflective surface either at a liquid/liquid interface or at an air/liquid interface by analogy with the reflective surfaces obtained with a low-melting point metal/metal alloy or with an aqueous colloidal preparation of metallic nanoparticles in presence of an appropriate ligand.
- the invention also relates to an organic-based metal-like liquid film (OMELLF), or liquid mirror, that comprises at least one compound according to the invention, more specifically a compound comprising one or more C 8 -C 20 saturated, linear or branched hydrocarbon chain comprising from 8 to 20 carbon atoms, including, but not limited to octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and the like, within which, in some more particular embodiments, one or more hydrogen atoms are replaced with a halogen atom.
- OELLF organic-based metal-like liquid film
- Liquid mirrors can be easily achieved notably by simple drop-casting or spraying of pure compound (dissolved in a suitable deposition medium) onto a stirred suitable fluid (e.g. pure water, an aqueous ion-saturated solution, ethylene glycol or another hydrophilic viscous fluid, silicone oil or another hydrophobic viscous fluid, ionic liquids) or by subsequent transfer of such a self-assembled reflective film.
- a suitable fluid e.g. pure water, an aqueous ion-saturated solution, ethylene glycol or another hydrophilic viscous fluid, silicone oil or another hydrophobic viscous fluid, ionic liquids
- the invention also relates to metal-like reflective coating that comprises at least one compound according to the invention.
- Reflectance spectra can be recorded with dedicated equipment in order to evaluate quantitatively the efficiency of the thin film to reflect light as a function of wavelength and incidence angle.
- the invention also relates to metal-like glittering surface that comprises at least one compound according to the invention.
- the range of application media for the pigments with special optical effects (and in some cases for their constitutive chromophores) according to the invention includes notably paints, coatings, printing inks, cosmetic formulations (e.g. nail lacquers) as well as implementations in the recreational and artistic (e.g. enamel) fields.
- Another possible application is the design of pigments for conception of new security inks that enter for example in the fabrication of banknotes, official identity documents, postage stamps, tax banderoles, security labels or product markings.
- Another possible application is the design of pigments and/or materials for the conception of new optical reflectors that enter for example in the fabrication of small mirrors for optics/microscopy/interferometry, sensors, very small mirrors for lasers (optical cavity) or mirrors for nomad and transportable devices.
- ⁇ X represents an oxygen or a sulfur atom
- ⁇ Ro to R 4 and Lx are as defined in any of the embodiments related to a compound of formula (I).
- the invention relates also to the use as dye or pigment of a compound of formula (lint).
- FIGURES are also to the use as dye or pigment of a compound of formula (lint).
- Figure 2 corresponds to a picture of a vivid yellow concentrated solution of compound 8 precursor-2 (left) in methylene chloride, and of a blue colored diluted solution (middle) and of an intense deep blue-purple concentrated solution (right) of compound 8-BTMA + both in acetonitrile.
- Figure 3 a corresponds to a picture (outside view) of a blue-purple lustrous thin film obtained on the wall of a glass container after simple evaporation of a solution of 8-BTMA + in acetonitrile.
- Figure 3b corresponds to a picture (inside view) of a blue-purple lustrous thin film obtained on the wall of a glass container after simple evaporation of a solution of 8-BTMA + in acetonitrile.
- Either halo or formyl moieties can be interconverted into aryl or alkyl groups e.g. under Suzuki cross-coupling or reductive conditions, respectively.
- the ketone is then reduced (e.g. by employing NaBFE or EhSiH in TFA) before a O-deprotection step to recover the phenol moieties.
- the resulting diphenol methylene can then be oxidized with DDQ (or another suitable oxidant, which is here more particularly a hydride abstraction reagent) to directly produce the desired quinone methide phenol.
- the target quinone methide phenolate is subsequently obtained by treatment with a suitable base (preferably an organic hydroxide base).
- a quinone methide phenol synthesized as described in previous procedures is engaged in a thionation reaction (e.g. by using the Lawesson’s reagent) [Vigalokl997]
- the corresponding thioquinone methide phenol is then reacted under basic conditions with dimethylthiocarbamoyl chloride.
- the resulting O-aryl /V, /V- d i m c t h y l c a r b a m o t h i o a t c is then submitted to an ambient- temperature Newman-Kwart rearrangement (e.g. by using an organic photooxidant as catalyst under blue- light irradiation) [Perkowski20l5]
- the target quinone methide phenolate is subsequently obtained by treatment with a suitable base (preferably an organic hydroxide base).
- a suitable base preferably an organic hydroxide base
- a protected polysubstituted phenol is />ara-brominated according to a classical procedure employing either Br2 or NBS as reactive species [Zysman2009]
- the resulting bromophenoxy precursor is then engaged in a lithiation reaction, and the intermediate is quenched with ethyl formate yielding a carbinol intermediate [Patents] which is subsequently oxidized to the corresponding ketone by using DDQ [Torricelli20l3]
- the protecting groups are then cleaved (e.g.
- a polysubstituted phenol precursor is engaged under either basic or acidic conditions in a formaldehyde-mediated dimerization reaction [Steelinkl968]
- the hydroxy groups of the resulting diphenol methylene are subsequently protected by triflate moieties to give the key methylene precursors KM.
- the previously described KM precursors may be engaged in a double Suzuki cross-coupling by reacting with an appropriately substituted phenylboronic acid/ester in presence of a base and a palladium catalyst.
- the resulting extended diphenol methylene is O- deprotected if needed and can then be oxidized with DDQ (or another suitable oxidant, which is here more particularly a hydride abstraction reagent) to directly produce the desired extended quinone methide phenol.
- DDQ or another suitable oxidant, which is here more particularly a hydride abstraction reagent
- the target extended quinone methide phenolate is subsequently obtained by treatment with a suitable base (preferably an organic hydroxide base).
- the resulting extended diphenol methylene can then be oxidized with DDQ (or another suitable oxidant, which is here more particularly a hydride abstraction reagent) to directly produce the desired styryl- extended quinone methide phenol.
- DDQ or another suitable oxidant, which is here more particularly a hydride abstraction reagent
- the target styryl- extended quinone methide phenolate is subsequently obtained by treatment with a suitable base (preferably an organic hydroxide base).
- the resulting extended benzophenone can then be reduced (by either NaBFb or EhSiH in TFA) before an O-deprotection step to recover the phenol moieties.
- the resulting phenethynyl- extended diphenol methylene can then be oxidized with DDQ (or another suitable oxidant, which is here more particularly a hydride abstraction reagent) to directly produce the desired phenethynyl- extended quinone methide phenol.
- DDQ or another suitable oxidant, which is here more particularly a hydride abstraction reagent
- the target phenethynyl- extended quinone methide phenolate is subsequently obtained by treatment with a suitable base (preferably an organic hydroxide base).
- the resulting phenethynyl- extended diphenol methylene can then be oxidized with DDQ (or another suitable oxidant, which is here more particularly a hydride abstraction reagent) to directly produce the desired phenethynyl- extended quinone methide phenol.
- DDQ or another suitable oxidant, which is here more particularly a hydride abstraction reagent
- the target phenethynyl- extended quinone methide phenolate is subsequently obtained by treatment with a suitable base (preferably an organic hydroxide base).
- a suitable base preferably an organic hydroxide base
- a persubstituted benzophenone bearing two protected phenol moieties in para- positions may be engaged in presence of an aryl organometallics [Harrerl975]
- the tertiary alcohol intermediate thus obtained is engaged in a O-deprotection step to directly produce the desired bridged-arylated quinone methide phenol to directly produce the desired bridged-arylated quinone methide phenol.
- a subsequent oxidation step with DDQ or another suitable oxidant, which is here more particularly a hydride abstraction reagent
- the target bridge-arylated quinone methide phenolate is subsequently obtained by treatment with a suitable base (preferably an organic hydroxide base).
- Reaction Scheme 8 bis A 2,3,5,6-tetrasubstituted phenol precursor is engaged in a dimerization in presence of a formylated aryl [Yamadal989]
- the resulting bridge- ary lated diphenol methylene can then be oxidized with DDQ (or another suitable oxidant, which is here more particularly a hydride abstraction reagent) to directly produce the desired bridged quinone methide phenol.
- DDQ or another suitable oxidant, which is here more particularly a hydride abstraction reagent
- the target bridge-arylated quinone methide phenolate is subsequently obtained by treatment with a suitable base (preferably an organic hydroxide base).
- a we/fl-brominated trisubstituted phenol precursor is engaged in a formaldehyde-mediated dimerization reaction to give the corresponding dibromo diphenol methylene [Best20l3]
- the hydroxyl moieties are then protected and bromine atoms are exchanged in presence of BuLi in order to produce the corresponding dilithium intermediate which is quenched by addition of a disubstituted silicon dichloride reagent [Best20l3]
- the resulting SiR2-bridged diphenol methylene is then oxidized with DDQ or /2-chloranil (or another suitable oxidant, which is here more particularly a hydride abstraction reagent) to directly produce the desired SiR2-bridged quinone methide phenol.
- the target SiR2-bridged quinone methide phenolate is subsequently obtained by treatment with a suitable base (preferably an organic hydroxide base).
- a protected me/a-brominated trisubstituted phenol precursor is engaged in a halogen-metal exchange reaction to produce the corresponding lithiated intermediate which is quenched by addition of dry acetone.
- the resulting tertiary alcohol is then dehydrated by heating in presence of KHSO4 to give a methylene exo compound.
- the latter molecule is engaged with a closely related counterpart (but bearing a benzylic alcohol moiety) in a sequence of reactions allowing coupling and bridging of these two parts [Pastierik20l4]
- the resulting CIVfe-bridged diphenol methylene is then oxidized with DDQ or /?-chloranil (or another suitable oxidant, which is here more particularly a hydride abstraction reagent) to directly produce the desired GVfe-bridged quinone methide phenol.
- the target GVfe-bridged quinone methide phenolate is subsequently obtained by treatment with a suitable base (preferably an organic hydroxide base).
- a para- hydroxy trisubstituted benzyl alcohol precursor is engaged in a Lewis acid-mediated dimerization with an appropriate meta- bromo trisubstituted phenol to give a bromo diphenol methylene which hydroxyl groups are subsequently protected.
- a halogen-metal exchange reaction step then allows production of the corresponding lithiated intermediate which is quenched by addition of dry acetone.
- the resulting tertiary alcohol is then dehydrated by heating in presence of KHSO4 to give a methylene exo compound that allows access to the corresponding GVfe-bridged methylene after a Lewis acid-mediated cyclization step.
- the resulting GVfe-bridged diphenol methylene is then oxidized with DDQ or /7-chloranil (or another suitable oxidant, which is here more particularly a hydride abstraction reagent) to directly produce the desired CIVfe-bridged quinone methide phenol.
- DDQ or /7-chloranil or another suitable oxidant, which is here more particularly a hydride abstraction reagent
- the target GVfe-bridged quinone methide phenolate is subsequently obtained by treatment with a suitable base (preferably an organic hydroxide base).
- the resulting bridged benzophenone is then engaged in a reduction to methylene (e.g. by employing NaBFb or EhSiH in TFA) followed by a deprotection step to recover the phenol moieties.
- the resulting bridged diphenol methylene can then be oxidized with DDQ (or another suitable oxidant, which is here more particularly a hydride abstraction reagent) to directly produce the desired bridged quinone methide phenol.
- the target bridged quinone methide phenolate is subsequently obtained by treatment with a suitable base (preferably an organic hydroxide base).
- a 2,3,5,6-tetrasubstituted phenol precursor is engaged in a dimerization in presence of an alkanal [Singh20l4]
- the resulting bridge-alkylated methylene can then be oxidized with DDQ (or another suitable oxidant, which is here more particularly a hydride abstraction reagent) to directly produce the desired bridge-alkylated quinone methide phenol.
- DDQ or another suitable oxidant, which is here more particularly a hydride abstraction reagent
- the target bridge- alkylated quinone methide phenolate is subsequently obtained by treatment with a suitable base (preferably an organic hydroxide base).
- a 2,6-disubstituted phenol precursor is engaged in a dimerization reaction in presence of an alkanal [Singh20l4]
- the resulting bridge-alkylated diphenol methylene can then be either halogenated (e.g. brominated with Br2 or NBS) or formylated (e.g. under Vilsmeier (POCI3, DMF) or Duff (methenamine, base) conditions) on the vacant 3,5 positions.
- halogenated e.g. brominated with Br2 or NBS
- formylated e.g. under Vilsmeier (POCI3, DMF) or Duff (methenamine, base) conditions
- Either halo or formyl moieties can be interconverted into aryl or alkyl groups e.g. under, respectively, Suzuki cross-coupling or reductive conditions.
- a persubstituted quinone methide phenol compound (previously O-protected) is engaged in a cyanation reaction, employing either KCN or another cyanide salt.
- the resulting cyano methylene compound can then be deprotected and oxidized with DDQ (or another suitable oxidant, which is here more particularly a hydride abstraction reagent) to produce the corresponding bridge-cyanated quinone methide phenol.
- DDQ or another suitable oxidant, which is here more particularly a hydride abstraction reagent
- the target bridge-cyanated quinone methide phenolate is subsequently obtained by treatment with a suitable base (preferably an organic hydroxide base).
- Either halo or formyl moieties can be interconverted into aryl or alkyl groups, e.g. under Suzuki cross-coupling or reductive conditions, respectively.
- the ketone is then submitted to a reductive amination procedure (e.g. by employing TiCL t in the first step and NaBFFCN in the second one) [Rahman2004] before a O-deprotection step to recover the phenol moieties.
- the resulting amino-bridge diphenol methylene can then be oxidized with DDQ (or another suitable oxidant, which is here more particularly a hydride abstraction reagent) to directly produce the desired quinone methide phenol.
- the target quinone methide phenolate is subsequently obtained by treatment with a suitable base (preferably an organic hydroxide base).
- Torricelli20l3 Torricelli, F., Bosson, J., Besnard, C., Chekini, M., Biirgi, T., Lacour, J.
- Methylene chloride is added and the organic phases gathered, dried on MgS0 4 and evaporated in vacuo to yield an orange/yellow solid which is purified via the Biotage lsolera One (silica-packed snap cartridge; 0-50% CH2Cl2/cyclohexane) to afford a yellow microcristalline solid (0.026 g, 15%).
- Absorbance of compound 8-BTMA + was measured in a 1 cm optical path quartz cuvette (against reference 1 cm optical path quartz cuvette containing pure acetonitrile) in a double beam Cary 500 spectrophotometer (Varian).
- the compound according to the invention is characterized by a single absorption band in the visible region of the electromagnetic spectrum.
- chromophoric properties of compounds of the invention or of their precursor of neutral charge of formula (Iiziet) as mentioned in the above description are directly observed from these solutions.
- a vivid yellow color is observed for 8 precursor-2, dissolved in methylene chloride and an intense deep blue-purple color is observed for 8-BTMA + , dissolved in acetonitrile.
- Figures 3a & 3b corresponds to pictures of a blue-purple lustrous thin film obtained on the wall of a container after simple evaporation of a solution of 8-BTMA + in acetonitrile.
- Such luster effects are characteristic of chromophores displaying a single sharp absorption band in the visible region of the electromagnetic spectrum, and a high molar extinction coefficient, as the compounds according to the invention.
- the compounds according to the invention are soluble in most organic (polar and non polar) solvents.
- organic solvents for example, an acetonitrile (CH 3 CN) solution of a compound of the invention (for example at a concentration of 5 mg/mL) can be prepared.
- This solution is spin-coated onto a substrate, and after solvent evaporation under ambient conditions, a uniform film exhibiting a reflective appearance is obtained.
- Films of different thicknesses can be spin-coated by varying the spin-coating speed or acceleration or duration, or by varying the concentration or the volume of the solution that is deposited onto the substrate. Also, several layers of films can be superimposed by repeating successive steps of spin coating as above.
- a solution of one of the compounds (around 1 Omg/mL or more) is dropwise added into a stirred saturated salt solution (e.g. ammonium salt).
- a stirred saturated salt solution e.g. ammonium salt.
- a homogeneous reflective film covers the liquid surface, that can if needed be carefully transferred onto another surface.
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EP18305893.2A EP3590914A1 (en) | 2018-07-05 | 2018-07-05 | Molecular organic materials derived from anionic para-quinone methide dyes and the like, with special optical effects |
PCT/EP2019/068147 WO2020008051A1 (en) | 2018-07-05 | 2019-07-05 | Molecular organic materials derived from anionic para-quinone methide dyes and the like, with special optical effects |
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EP18305893.2A Withdrawn EP3590914A1 (en) | 2018-07-05 | 2018-07-05 | Molecular organic materials derived from anionic para-quinone methide dyes and the like, with special optical effects |
EP19741981.5A Pending EP3818035A1 (en) | 2018-07-05 | 2019-07-05 | Molecular organic materials derived from anionic para-quinone methide dyes and the like, with special optical effects |
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CA2311064A1 (en) | 1999-06-18 | 2000-12-18 | The Governors Of The University Of Alberta | Substituted tetraarylethylene compounds |
US6764187B2 (en) | 2000-12-22 | 2004-07-20 | The Regents Of The University Of California | Universally oriented renewable liquid mirror |
CA2424825C (en) | 2002-04-10 | 2010-10-05 | Universite Laval | Deformable reflecting mirrors from metallic surface layers deposited on liquids |
CA2428135C (en) | 2002-05-07 | 2011-04-19 | Ermanno Borra | Reflecting mirrors shaped with magnetic fields |
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