JP6796749B2 - New fluorescent compound and fluorescent composition containing it - Google Patents
New fluorescent compound and fluorescent composition containing it Download PDFInfo
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- JP6796749B2 JP6796749B2 JP2017013305A JP2017013305A JP6796749B2 JP 6796749 B2 JP6796749 B2 JP 6796749B2 JP 2017013305 A JP2017013305 A JP 2017013305A JP 2017013305 A JP2017013305 A JP 2017013305A JP 6796749 B2 JP6796749 B2 JP 6796749B2
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- 239000000203 mixture Substances 0.000 title claims description 46
- 239000007850 fluorescent dye Substances 0.000 title description 7
- 150000001875 compounds Chemical class 0.000 claims description 166
- 150000003839 salts Chemical class 0.000 claims description 60
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 41
- 239000002253 acid Substances 0.000 claims description 38
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 239000012453 solvate Substances 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 17
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 14
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 13
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 12
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- HZXJVDYQRYYYOR-UHFFFAOYSA-K scandium(iii) trifluoromethanesulfonate Chemical compound [Sc+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HZXJVDYQRYYYOR-UHFFFAOYSA-K 0.000 claims description 10
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 10
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- 229910015900 BF3 Inorganic materials 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 7
- 239000003495 polar organic solvent Substances 0.000 claims description 7
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 6
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 6
- 125000003107 substituted aryl group Chemical group 0.000 claims description 6
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims description 6
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 6
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 5
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 4
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 4
- 238000010586 diagram Methods 0.000 claims description 3
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 3
- 238000007614 solvation Methods 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 72
- -1 acids Compound Chemical class 0.000 description 46
- 238000006243 chemical reaction Methods 0.000 description 19
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- 238000000862 absorption spectrum Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 6
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 6
- HFAHKTWOAXPIAP-UHFFFAOYSA-N 2-[4-(3,4-diethyl-1H-pyrrol-2-yl)phenyl]-3,4-diethyl-1H-pyrrole Chemical compound CCc1c[nH]c(c1CC)-c1ccc(cc1)-c1[nH]cc(CC)c1CC HFAHKTWOAXPIAP-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- HSFRGIWWFULHHK-UHFFFAOYSA-N C1(=CC=C(C=C1)C1=C(C(=C(N1)C=O)CC)CC)C1=C(C(=C(N1)C=O)CC)CC Chemical compound C1(=CC=C(C=C1)C1=C(C(=C(N1)C=O)CC)CC)C1=C(C(=C(N1)C=O)CC)CC HSFRGIWWFULHHK-UHFFFAOYSA-N 0.000 description 5
- 239000002841 Lewis acid Substances 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 5
- 125000002252 acyl group Chemical group 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
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- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 3
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
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- 150000007522 mineralic acids Chemical class 0.000 description 2
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 2
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- 239000007858 starting material Substances 0.000 description 2
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- 125000004739 (C1-C6) alkylsulfonyl group Chemical group 0.000 description 1
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- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 238000004252 FT/ICR mass spectrometry Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000005874 Vilsmeier-Haack formylation reaction Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000005530 alkylenedioxy group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000748 anthracen-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([H])=C([*])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
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- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([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
- 239000003599 detergent Substances 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000006125 ethylsulfonyl group Chemical group 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 230000022244 formylation Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 125000003104 hexanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 125000005524 levulinyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000001038 naphthoyl group Chemical group C1(=CC=CC2=CC=CC=C12)C(=O)* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
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- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Landscapes
- Pyrrole Compounds (AREA)
Description
本発明は、蛍光色素として有用な、ベンゼン環架橋ビピロール構造を有する新規な化合物、及びそれを含有する蛍光組成物に関する。本発明はまた、単一分子で白色蛍光を示す、上記化合物を含有する蛍光組成物に関する。 The present invention relates to a novel compound having a benzene ring-crosslinked bipyrrole structure useful as a fluorescent dye, and a fluorescent composition containing the same. The present invention also relates to a fluorescent composition containing the above compound, which exhibits white fluorescence with a single molecule.
白色蛍光は、通常、赤、緑、青色の光の三原色のうちの複数の蛍光色素を混合することにより得ることが可能である。しかし、それら蛍光色素である無機化合物や有機化合物は、それぞれ異なる励起波長及び蛍光量子収率を持つことから、白色蛍光を得るためには、色素混合比や励起波長等において、極めて制約された条件が求められるという問題点を有していた。また、蛍光色素は、それぞれ化合物の耐久性も異なることから、それらのバランスを維持して、白色蛍光が得られる状態を長期間維持することは難しく、それ故、その製品化においては、煩雑な条件検討が必要であり、製品価格も増大する等の多くの技術的困難性を有していた。
一方、単一分子で白色蛍光を実現することができれば、より簡便且つ効果的な蛍光色素となり得ることが予想される。しかし、単一分子で白色蛍光を実現できる化合物は、これまで殆ど報告されておらず、本発明者らが知る限りでは、アリール基を有するオキサジアゾール化合物（特許文献１、２）、並びに酸の添加により白色蛍光を発現する、特定のアミノチアゾール構造（非特許文献１）又は特定のジチエノ［３，２−ｂ：２’，３’−ｄ］ホスホール構造（非特許文献２）を有する化合物についての報告例のみである。
White fluorescence can usually be obtained by mixing a plurality of fluorescent dyes among the three primary colors of red, green and blue light. However, since the inorganic compounds and organic compounds that are these fluorescent dyes have different excitation wavelengths and fluorescence quantum yields, in order to obtain white fluorescence, extremely restricted conditions such as the dye mixing ratio and the excitation wavelength are obtained. Had the problem that was required. In addition, since the durability of each compound is different for each fluorescent dye, it is difficult to maintain the balance between them and maintain a state in which white fluorescence can be obtained for a long period of time. Therefore, it is complicated to commercialize the fluorescent dye. It was necessary to study the conditions, and there were many technical difficulties such as an increase in the product price.
On the other hand, if white fluorescence can be realized with a single molecule, it is expected that a simpler and more effective fluorescent dye can be obtained. However, few compounds capable of achieving white fluorescence with a single molecule have been reported so far, and as far as the present inventors know, oxadiazole compounds having an aryl group (Patent Documents 1 and 2), and acids Compound having a specific aminothiazole structure (Non-Patent Document 1) or a specific dithieno [3,2-b: 2', 3'-d] phosphor structure (Non-Patent Document 2) that expresses white fluorescence by the addition of It is only a report example about.
このような背景のもと、耐久性が高く、簡便且つ安価に高品質の白色蛍光が実現できる実用的な蛍光素子の開発がますます求められている。 Against this background, there is an increasing demand for the development of practical fluorescent elements that are highly durable, can easily and inexpensively realize high-quality white fluorescence.
本発明の目的は、単一分子で白色蛍光を含め多彩な蛍光色を発現することができ、且つ耐久性にもコスト的にも優れた実用的な蛍光素子として有用な新規化合物、及びそれを含有する蛍光組成物を提供することである。 An object of the present invention is a novel compound that can express various fluorescent colors including white fluorescence with a single molecule and is useful as a practical fluorescent element having excellent durability and cost, and a novel compound thereof. It is to provide a fluorescent composition containing.
本発明者らは、かかる状況下、鋭意検討を重ねた結果、下記式（Ｉ）： As a result of diligent studies under such circumstances, the present inventors have obtained the following formula (I):
[式中、
Ｒ１及びＲ１’は、それぞれ独立して、水素原子、置換されていてもよいアルキル基、置換されていてもよいシクロアルキル基又は置換されていてもよいアリール基を示し、
Ｒ２、Ｒ２’ 、Ｒ３及びＲ３’は、それぞれ独立して、水素原子又は置換されていてもよいアルキル基を示し、
ｎ個のＲは、それぞれ独立して、アルキル基を示し、並びに
ｎは、０〜４の整数を示す。]
で表される化合物（以下、「化合物（Ｉ）」と称することもある。）又はその塩、或いはそれらの溶媒和物が、酸を特定の当量比で添加するという簡便な操作により発光色を微調整することができ、多彩な蛍光発光、特に、白色蛍光発光、を実現できることを見出し、本発明を完成するに至った。
[During the ceremony,
R 1 and R 1 'are each independently a hydrogen atom, a optionally substituted alkyl group, an optionally substituted cycloalkyl group or an optionally substituted aryl group,
R 2, R 2 ', R 3 and R 3' each independently represent a hydrogen atom or an optionally substituted alkyl group,
Each of the n Rs independently represents an alkyl group, and n represents an integer from 0 to 4. ]
The compound represented by (hereinafter, also referred to as "Compound (I)") or a salt thereof, or a solvate thereof, gives a luminescent color by a simple operation of adding an acid at a specific equivalent ratio. We have found that it is possible to make fine adjustments and realize a variety of fluorescence emission, particularly white fluorescence emission, and have completed the present invention.
すなわち、本発明は以下の通りである。
［１］式（Ｉ）：
That is, the present invention is as follows.
[1] Equation (I):
[式中、
Ｒ１及びＲ１’は、それぞれ独立して、水素原子、置換されていてもよいアルキル基、置換されていてもよいシクロアルキル基又は置換されていてもよいアリール基を示し、
Ｒ２、Ｒ２’ 、Ｒ３及びＲ３’は、それぞれ独立して、水素原子又は置換されていてもよいアルキル基を示し、
ｎ個のＲは、それぞれ独立して、アルキル基を示し、並びに
ｎは、０〜４の整数を示す。]
で表される化合物又はその塩、或いはそれらの溶媒和物、
［２］Ｒ２、Ｒ２’ 、Ｒ３及びＲ３’が、それぞれ独立して、Ｃ１−６アルキル基であり、且つｎが０である、上記［１］に記載の化合物又はその塩、或いはそれらの溶媒和物、
［３］Ｒ１及びＲ１’が、それぞれ独立して、アリール基又はＣ１−２０アルキル基である、上記［１］又は［２］に記載の化合物又はその塩、或いはそれらの溶媒和物、
［４］Ｒ１及びＲ１’が、共にフェニル基又はＣ１−６アルキル基である、上記［３］に記載の化合物又はその塩、或いはそれらの溶媒和物、
［５］式（Ｉａ）：
[During the ceremony,
R 1 and R 1 'are each independently a hydrogen atom, a optionally substituted alkyl group, an optionally substituted cycloalkyl group or an optionally substituted aryl group,
R 2, R 2 ', R 3 and R 3' each independently represent a hydrogen atom or an optionally substituted alkyl group,
Each of the n Rs independently represents an alkyl group, and n represents an integer from 0 to 4. ]
Compounds represented by, or salts thereof, or solvates thereof,
[2] R 2, R 2 ', R 3 and R 3' are each independently a C 1-6 alkyl group, and n is 0, or a salt thereof according to [1] Or their solvates,
[3] R 1 and R 1 'are each independently an aryl group or a C 1-20 alkyl group, the above-mentioned [1] or a compound or a salt thereof according to [2], or their solvate ,
[4] R 1 and R 1 ', are both phenyl group or a C 1-6 alkyl group, the compound or a salt thereof, or a solvate thereof according to [3],
[5] Equation (Ia):
又は式（Ｉｂ）： Or formula (Ib):
で表される、上記［１］に記載の化合物又はその塩、或いはそれらの溶媒和物、
［６］上記［１］〜［５］のいずれかに記載の化合物及びその塩を含有する蛍光組成物、
［７］その塩が、塩酸、酢酸、トリフルオロ酢酸、トリクロロ酢酸、プロピオン酸、硝酸、硫酸、過塩素酸、フッ化水素、塩化水素、臭化水素、ヨウ化水素、ｐ−トルエンスルホン酸、トリフルオロメタンスルホン酸、ヘキサフルオロ−２−プロパノール、トリフルオロメタンスルホン酸スカンジウム、フッ化テトラ−ｎ−ブチルアンモニウム、塩化テトラ−ｎ−ブチルアンモニウム、臭化テトラ−ｎ−ブチルアンモニウム、ヨウ化テトラ−ｎ−ブチルアンモニウム、塩化アルミニウム、三塩化ホウ素、三フッ化ホウ素、塩化ガリウム及びトリス（ペンタフルオロフェニル）ホウ素からなる群より選択される酸との塩である、上記［６］に記載の蛍光組成物、
［８］その塩が、塩酸、トリフルオロ酢酸、硝酸、硫酸、塩化テトラ−ｎ−ブチルアンモニウム又は臭化テトラ−ｎ−ブチルアンモニウムとの塩である、上記［６］に記載の蛍光組成物、
［９］上記［５］に記載の化合物、及びその塩酸、トリフルオロ酢酸、硝酸、硫酸、塩化テトラ−ｎ−ブチルアンモニウム又は臭化テトラ−ｎ−ブチルアンモニウムとの塩を含有し、ＣＩＥ（１９３１）色度図における色度座標（ｘ，ｙ）が、（０．３２〜０．３４，０．３２〜０．３４）である、白色蛍光組成物、
［１０］上記［５］に記載の化合物と、塩酸、トリフルオロ酢酸、硝酸又は硫酸とを非極性有機溶媒中で当量比１：０．７〜１：１で混合してなる、白色蛍光組成物、
［１１］上記［５］に記載の化合物と、塩化テトラ−ｎ−ブチルアンモニウム又は臭化テトラ−ｎ−ブチルアンモニウムとを当量比１：５００で混合してなる、白色蛍光組成物、等に関する。
The compound according to the above [1] or a salt thereof, or a solvate thereof, represented by
[6] A fluorescent composition containing the compound according to any one of [1] to [5] above and a salt thereof.
[7] The salt thereof is hydrochloric acid, acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, nitrate, sulfuric acid, perchloric acid, hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, p-toluenesulfonic acid, Trifluoromethanesulfonic acid, hexafluoro-2-propanol, scandium trifluoromethanesulfonate, tetra-n-butylammonium fluoride, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-iodide The fluorescent composition according to the above [6], which is a salt with an acid selected from the group consisting of butylammonium, aluminum chloride, boron trifluoride, boron trifluoride, gallium chloride and tris (pentafluorophenyl) boron.
[8] The fluorescent composition according to the above [6], wherein the salt is a salt with hydrochloric acid, trifluoroacetic acid, nitric acid, sulfuric acid, tetra-n-butylammonium chloride or tetra-n-butylammonium bromide.
[9] The compound according to the above [5] and a salt thereof with hydrochloric acid, trifluoroacetic acid, nitric acid, sulfuric acid, tetra-n-butylammonium chloride or tetra-n-butylammonium bromide, and CIE (1931). ) The white fluorescent composition, wherein the chromaticity coordinates (x, y) in the chromaticity diagram are (0.32 to 0.34, 0.32 to 0.34).
[10] A white fluorescent composition obtained by mixing the compound according to [5] above with hydrochloric acid, trifluoroacetic acid, nitric acid or sulfuric acid in a non-polar organic solvent at an equivalent ratio of 1: 0.7 to 1: 1. Stuff,
[11] The present invention relates to a white fluorescent composition obtained by mixing the compound according to the above [5] with tetra-n-butylammonium chloride or tetra-n-butylammonium bromide at an equivalent ratio of 1: 500.
本発明によれば、酸を特定の当量比で添加するという簡便な操作により単一分子で白色蛍光を含め多彩な蛍光色を発現することができ、且つ耐久性にもコスト的にも優れた実用的な蛍光素子として有用な新規化合物（化合物（Ｉ）又はその塩）及びそれを含有する蛍光組成物を提供することができる。 According to the present invention, a variety of fluorescent colors including white fluorescence can be expressed with a single molecule by a simple operation of adding an acid at a specific equivalent ratio, and the durability and cost are excellent. It is possible to provide a novel compound (compound (I) or a salt thereof) useful as a practical fluorescent element and a fluorescent composition containing the same.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
（定義） (Definition)
本明細書中、「ハロゲン原子」とは、フッ素原子、塩素原子、臭素原子又はヨウ素原子を意味する。 In the present specification, the "halogen atom" means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
本明細書中、「置換されていてもよいアルキル基」における「アルキル基」としては、直鎖状又は分岐鎖状の炭素原子数１以上のアルキル基を意味し、特に炭素数範囲の限定がない場合には、好ましくは、Ｃ１−２０アルキル基であり、中でも、Ｃ１−１２アルキル基がより好ましく、Ｃ１−６アルキル基が特に好ましい。 In the present specification, the "alkyl group" in the "optionally substituted alkyl group" means a linear or branched alkyl group having one or more carbon atoms, and the carbon number range is particularly limited. If not, it is preferably a C 1-20 alkyl group, with a C 1-12 alkyl group being more preferred and a C 1-6 alkyl group being particularly preferred.
本明細書中、「Ｃ１−２０アルキル基」とは、直鎖又は分岐鎖の炭素原子数１〜２０のアルキル基を意味し、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、ペンチル、イソペンチル、ネオペンチル、１−エチルプロピル、ヘキシル、イソヘキシル、１，１−ジメチルブチル、２，２−ジメチルブチル、３，３−ジメチルブチル、２−エチルブチル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、エイコシル等が挙げられる。 In the present specification, the “C 1-20 alkyl group” means an alkyl group having 1 to 20 carbon atoms in a straight chain or a branched chain, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec. -Butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, octyl , Nonyl, decyl, undecyl, dodecyl, tridecyl, eikosyl and the like.
本明細書中、「Ｃ１−１２アルキル基」とは、直鎖又は分岐鎖の炭素原子数１〜１２のアルキル基を意味し、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、ペンチル、イソペンチル、ネオペンチル、１−エチルプロピル、ヘキシル、イソヘキシル、１，１−ジメチルブチル、２，２−ジメチルブチル、３，３−ジメチルブチル、２−エチルブチル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル等が挙げられる。 In the present specification, the “C 1-12 alkyl group” means an alkyl group having 1 to 12 carbon atoms in a straight chain or a branched chain, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec. -Butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, octyl , Nonyl, decyl, undecyl, dodecyl and the like.
本明細書中、「Ｃ１−６アルキル基」とは、直鎖又は分岐鎖の炭素原子数１〜６のアルキル基を意味し、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、ペンチル、イソペンチル、ネオペンチル、１−エチルプロピル、ヘキシル、イソヘキシル、１，１−ジメチルブチル、２，２−ジメチルブチル、３，３−ジメチルブチル、２−エチルブチル等が挙げられる。 In the present specification, the “C 1-6 alkyl group” means an alkyl group having 1 to 6 carbon atoms in a straight chain or a branched chain, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec. -Butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl and the like. ..
本明細書中、「Ｃ１−４アルキル基」とは、直鎖又は分岐鎖の炭素原子数１〜４のアルキル基を意味し、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル等が挙げられる。 In the present specification, the “C 1-4 alkyl group” means an alkyl group having 1 to 4 carbon atoms in a straight chain or a branched chain, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec. -Butyl, tert-butyl and the like can be mentioned.
本明細書中、「Ｃ１−６アルコキシ基」とは、直鎖又は分岐鎖の炭素原子数１〜６のアルコキシ基を意味し、例えば、メトキシ、エトキシ、プロポキシ、イソプロポキシ、ブトキシ、イソブトキシ、ｓｅｃ−ブトキシ、ｔｅｒｔ−ブトキシ、ペンチルオキシ、イソペンチルオキシ、ネオペンチルオキシ、ヘキシルオキシ等が挙げられる。中でも、Ｃ１−４アルコキシ基が好ましい。 In the present specification, the "C 1-6 alkoxy group" means an alkoxy group having 1 to 6 carbon atoms in a linear or branched chain, and for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and the like. Examples thereof include sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy and the like. Of these, the C 1-4 alkoxy group is preferable.
本明細書中、「置換されていてもよいシクロアルキル基」における「シクロアルキル基」としては、環を構成する炭素原子数３以上のシクロアルキル基を意味し、特に炭素数範囲の限定がない場合には、好ましくは、Ｃ３−１０シクロアルキル基である。 In the present specification, the "cycloalkyl group" in the "optionally substituted cycloalkyl group" means a cycloalkyl group having 3 or more carbon atoms constituting the ring, and the carbon number range is not particularly limited. In some cases, it is preferably a C 3-10 cycloalkyl group.
本明細書中、「Ｃ３−１０シクロアルキル基」としては、例えば、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチル等が挙げられる。中でも、Ｃ３−８シクロアルキル基が好ましく、Ｃ３−６シクロアルキル基がより好ましく、シクロペンチル基又はシクロヘキシル基が特に好ましい。 In the present specification, examples of the "C 3-10 cycloalkyl group" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. Of these, a C 3-8 cycloalkyl group is preferable, a C 3-6 cycloalkyl group is more preferable, and a cyclopentyl group or a cyclohexyl group is particularly preferable.
上記のＣ３−１０シクロアルキル基は、ベンゼン環と縮合して縮合環基を形成していてもよく、このような縮合環基としては、例えば、インダニル、テトラヒドロナフチル、フルオレニル等が挙げられる。 The above-mentioned C 3-10 cycloalkyl group may be condensed with a benzene ring to form a condensed ring group, and examples of such a condensed ring group include indanyl, tetrahydronaphthyl, fluorenyl and the like.
また、上記のＣ３−１０シクロアルキル基は、Ｃ７−１０橋かけ式炭化水素基であってもよい。Ｃ７−１０橋かけ式炭化水素基としては、ビシクロ［２．２．１］ヘプチル（ノルボルニル）、ビシクロ［２．２．２］オクチル、ビシクロ［３．２．１］オクチル、アダマンチル等が挙げられる。 Further, the above C 3-10 cycloalkyl group may be a C 7-10 cross-linked hydrocarbon group. Examples of the C 7-10 bridging hydrocarbon group include bicyclo [2.2.1] heptyl (norbornyl), bicyclo [2.2.2] octyl, bicyclo [3.2.1] octyl, adamantyl and the like. Be done.
さらに、上記のＣ３−１０シクロアルキル基は、Ｃ３−１０シクロアルカンとスピロ環基を形成していてもよい。ここで、Ｃ３−１０シクロアルカンとしては、上記のＣ３−１０シクロアルキル基に対応する環が挙げられる。このようなスピロ環基としては、スピロ［４．５］デカン−８−イル等が挙げられる。 Further, the above C 3-10 cycloalkyl group may form a spiro ring group with C 3-10 cycloalkane. Here, as the C 3-10 cycloalkane, ring corresponding to C 3-10 cycloalkyl groups mentioned above. Examples of such a spiro ring group include spiro [4.5] decane-8-yl and the like.
本明細書中、「置換されていてもよいアリール基」における「アリール基」としては、芳香族性を示す単環式或いは多環式（縮合）の炭化水素基を意味し、具体的には、例えば、フェニル、１−ナフチル、２−ナフチル、ビフェニル、ターフェニル、ジフェニルナフチル、２−アンスリル、フェナントリル等のＣ６−２２アリール基を示す。中でも、Ｃ６−１０アリール基が好ましい。 In the present specification, the "aryl group" in the "optionally substituted aryl group" means a monocyclic or polycyclic (condensed) hydrocarbon group exhibiting aromaticity, and specifically, , For example, C 6-22 aryl groups such as phenyl, 1-naphthyl, 2-naphthyl, biphenyl, terphenyl, diphenylnaphthyl, 2-anthryl, phenanthryl and the like. Of these, a C 6-10 aryl group is preferable.
本明細書中、「Ｃ６−１０アリール基」としては、例えば、フェニル、１−ナフチル、２−ナフチルが挙げられ、フェニルが特に好ましい。 In the present specification, examples of the "C 6-10 aryl group" include phenyl, 1-naphthyl and 2-naphthyl, with phenyl being particularly preferred.
上記のＣ６−１０アリール基は、Ｃ３−１０シクロアルカンと縮合して縮合環基を形成していてもよく、このような縮合環基としては、例えば、インダニル、テトラヒドロナフチル等が挙げられる。 The above C 6-10 aryl group may be condensed with C 3-10 cycloalkane to form a condensed ring group, and examples of such a condensed ring group include indanyl, tetrahydronaphthyl and the like. ..
本明細書中、「アラルキル基」とは、前記した「アルキル基」に前記した「アリール基」が置換した基を意味し、好ましくは、「Ｃ７−１４アラルキル基」である。 In the present specification, the "aralkyl group" means a group in which the above-mentioned "alkyl group" is substituted with the above-mentioned "aryl group", and is preferably "C 7-14 aralkyl group".
本明細書中、「Ｃ７−１４アラルキル基」とは、「Ｃ１−４アルキル基」に「Ｃ６−１０アリール基」が置換した基を意味し、例えば、ベンジル、１−フェニルエチル、２−フェニルエチル、（ナフチル−１−イル）メチル、（ナフチル−２−イル）メチル、１−（ナフチル−１−イル）エチル、１−（ナフチル−２−イル）エチル、２−（ナフチル−１−イル）エチル、２−（ナフチル−２−イル）エチル、ビフェニリルメチル等が挙げられ、ベンジルが特に好ましい。 In the present specification, the "C 7-14 aralkyl group" means a group in which a "C 1-4 alkyl group" is substituted with a "C 6-10 aryl group", for example, benzyl, 1-phenylethyl, and the like. 2-Phenylethyl, (naphthyl-1-yl) methyl, (naphthyl-2-yl) methyl, 1- (naphthyl-1-yl) ethyl, 1- (naphthyl-2-yl) ethyl, 2- (naphthyl-) Examples thereof include 1-yl) ethyl, 2- (naphthyl-2-yl) ethyl, biphenylylmethyl and the like, and benzyl is particularly preferable.
本明細書中、「アルキルスルホニル基」とは、−Ｓ（Ｏ）２−に「アルキル基」が結合した基を意味し、例えば、メチルスルホニル、エチルスルホニル、プロピルスルホニル、イソプロピルスルホニル、ブチルスルホニル、イソブチルスルホニル、ｓｅｃ−ブチルスルホニル、ｔｅｒｔ−ブチルスルホニル、ペンチルスルホニル、イソペンチルスルホニル、ネオペンチルスルホニル、ヘキシルスルホニル、ヘプチルスルホニル、オクチルスルホニル、ノニルスルホニル、デシルスルホニル、ウンデシルスルホニル、ドデシルスルホニル等のＣ１−２０アルキルスルホニル基が挙げられる。中でも、ドデシルスルホニル基が好ましい。 As used herein, the term "alkylsulfonyl group", -S (O) 2 - means the "alkyl group" is bonded groups, e.g., methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, C 1- such as isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, hexylsulfonyl, heptylsulfonyl, octylsulfonyl, nonylsulfonyl, decylsulfonyl, undecylsulfonyl, dodecylsulfonyl, etc. 20 Alkylsulfonyl groups can be mentioned. Of these, the dodecylsulfonyl group is preferable.
本明細書中、「アリールスルホニル基」とは、−Ｓ（Ｏ）２−に「アリール基」が結合した基を意味し、例えば、フェニルスルホニル、１−ナフチルスルホニル、２−ナフチルスルホニル等のＣ６−１０アリールスルホニル基が挙げられる。中でも、フェニルスルホニル基が好ましい。 In the present specification, the "arylsulfonyl group", -S (O) 2 - means the group "aryl group" is bonded, for example, phenylsulfonyl, 1-naphthylsulfonyl, and 2-naphthylsulfonyl C 6-10 arylsulfonyl groups are mentioned. Of these, a phenylsulfonyl group is preferable.
本明細書中、「アシル基」としては、例えば、直鎖状または分岐鎖状のＣ１−６アルカノイル基、Ｃ７−１３アロイル基等が挙げられる。具体的には、例えば、ホルミル、アセチル、ｎ−プロピオニル、イソプロピオニル、ｎ−ブチリル、イソブチリル、ピバロイル、バレリル、ヘキサノイル、ベンゾイル、ナフトイル、レブリニル等が挙げられ、これらはそれぞれ置換されていてもよい。 In the present specification, examples of the "acyl group" include linear or branched C 1-6 alkanoyl groups and C 7-13 aloyl groups. Specific examples thereof include formyl, acetyl, n-propionyl, isopropionyl, n-butyryl, isobutyryl, pivaloyl, valeryl, hexanoyl, benzoyl, naphthoyl, levulinyl and the like, and these may be substituted respectively.
本明細書中、「アシロキシ基」とは、ヒドロキシ基に前記した「アシル基」が置換した基を意味し、好ましくは、Ｃ１−６アルカノイロキシ基又はＣ７−１３アロイロキシ基等が挙げられる。具体的には、例えば、アセトキシ、ｎ−プロピオニロキシ、ピバロイロキシ、バレリロキシ、ヘキサノイロキシ、ベンゾイロキシ等が挙げられ、これらはそれぞれ置換されていてもよい。 In the present specification, the "acyloxy group" means a group in which the above-mentioned "acyl group" is substituted for a hydroxy group, and preferred examples thereof include a C 1-6 alkanoyloxy group and a C 7-13 alloyoxy group. Specifically, for example, acetoxy, n-propionibacterium, pivalolioxy, valeryloxy, hexanoyloxy, benzoyloxy and the like can be mentioned, and these may be substituted respectively.
本明細書中、「置換されていてもよい」とは、特に規定する場合を除き、１個以上の置換基を有していてもよいことを意味し、該「置換基」としては、（１）ハロゲン原子、（２）ニトロ基、（３）シアノ基、（４）ヒドロキシ基、（５）アシロキシ基、、（６）アシル基、（７）Ｃ１−６アルキル基、（８）Ｃ３−８シクロアルキル基、（９）Ｃ１−６アルコキシ基、（１０）Ｃ１−６アルキレンジオキシ基、（１１）Ｃ６−１０アリール基、（１２）Ｃ７−１４アラルキル基、（１３）Ｃ１−６アルキルスルホニル基、（１４）Ｃ６−１０アリールスルホニル基等が挙げられる。中でも、フッ素原子、塩素原子、Ｃ１−６アルキル、Ｃ１−６アルコキシ、メチレンジオキシ、フェニル、シクロヘキシル、ベンジル等が好ましい。また、複数の置換基が存在する場合、各置換基は、同一でも異なっていてもよい。 In the present specification, "may be substituted" means that it may have one or more substituents, unless otherwise specified, and the "substituent" includes ( 1) halogen atom, (2) nitro group, (3) cyano group, (4) hydroxy group, (5) acyloxy group, (6) acyl group, (7) C 1-6 alkyl group, (8) C 3-8 cycloalkyl group, (9) C 1-6 alkoxy group, (10) C 1-6 alkylenedioxy group, (11) C 6-10 aryl group, (12) C 7-14 aralkyl group, ( 13) C 1-6 alkylsulfonyl group, (14) C 6-10 arylsulfonyl group and the like can be mentioned. Among them, fluorine atom, chlorine atom, C 1-6 alkyl, C 1-6 alkoxy, methylenedioxy, phenyl, cyclohexyl, benzyl and the like are preferable. Further, when a plurality of substituents are present, each of the substituents may be the same or different.
上記置換基は、さらに上記（１）〜（１４）から選ばれる１個以上の置換基で置換されていてもよい。置換基の数は、置換可能な数であれば特に限定されないが、好ましくは、０個（すなわち無置換）、または１乃至３個である。 The substituent may be further substituted with one or more substituents selected from the above (1) to (14). The number of substituents is not particularly limited as long as it can be substituted, but is preferably 0 (that is, unsubstituted) or 1 to 3.
本明細書における「非極性有機溶媒」としては、具体的には、クロロホルム、ジクロロメタン、１，２−ジクロロエタン等のハロゲン系溶媒；ベンゼン、トルエン、キシレン、メシチレン等の芳香族系溶媒；ヘキサン、ペンタン、ヘプタン、オクタン、ノナン、シクロヘキサン等の脂肪族系溶媒；ジオキサン、テトラヒドロフラン等のエーテル系溶媒等が挙げられる。中でも、ジクロロメタン、クロロホルム、テトラヒドロフラン等が好ましい。 Specific examples of the "non-polar organic solvent" in the present specification include halogen-based solvents such as chloroform, dichloromethane and 1,2-dichloroethane; aromatic solvents such as benzene, toluene, xylene and mesitylene; hexane and pentane. , Heptan, octane, nonane, cyclohexane and other aliphatic solvents; and examples include ether solvents such as dioxane and tetrahydrofuran. Of these, dichloromethane, chloroform, tetrahydrofuran and the like are preferable.
本明細書中、化合物の「塩」としては、化合物（Ｉ）と塩を形成するものであればいかなる塩でもよく、例えば、無機酸との塩、有機酸との塩等のブレンステッド酸との塩、ルイス酸との塩等が挙げられる。
無機酸との塩としては、例えば、塩酸（又は塩化水素）、硝酸、硫酸、リン酸、臭化水素酸（又は臭化水素）、フッ化水素酸（又はフッ化水素）、ヨウ化水素酸（又はヨウ化水素）、過塩素酸等との塩が挙げられる。
有機酸との塩としては、例えば、酢酸、トリフルオロ酢酸、トリクロロ酢酸、プロピオン酸、シュウ酸、マレイン酸、クエン酸、フマル酸、乳酸、リンゴ酸、コハク酸、酒石酸、グルコン酸、アスコルビン酸、メタンスルホン酸、トリフルオロメタンスルホン酸、ベンゼンスルホン酸、p-トルエンスルホン酸、ヘキサフルオロ−２−プロパノール等との塩が挙げられる。
ルイス酸との塩としては、例えば、トリフルオロメタンスルホン酸スカンジウム、フッ化テトラ−ｎ−ブチルアンモニウム、塩化テトラ−ｎ−ブチルアンモニウム、臭化テトラ−ｎ−ブチルアンモニウム、ヨウ化テトラ−ｎ−ブチルアンモニウム、塩化アルミニウム、三塩化ホウ素、三フッ化ホウ素、塩化ガリウム及びトリス（ペンタフルオロフェニル）ホウ素等との塩が挙げられる。
化合物（Ｉ）の塩は、好ましくは、化合物（Ｉ）１分子に対して、上記酸が１分子又は２分子付加した塩である。
化合物（Ｉ）の塩としては、好ましくは、塩酸、酢酸、トリフルオロ酢酸、トリクロロ酢酸、プロピオン酸、硝酸、硫酸、過塩素酸、フッ化水素、塩化水素、臭化水素、ヨウ化水素、ｐ−トルエンスルホン酸、トリフルオロメタンスルホン酸、ヘキサフルオロ−２−プロパノール、トリフルオロメタンスルホン酸スカンジウム、フッ化テトラ−ｎ−ブチルアンモニウム、塩化テトラ−ｎ−ブチルアンモニウム、臭化テトラ−ｎ−ブチルアンモニウム、ヨウ化テトラ−ｎ−ブチルアンモニウム、塩化アルミニウム、三塩化ホウ素、三フッ化ホウ素、塩化ガリウム及びトリス（ペンタフルオロフェニル）ホウ素からなる群より選択される酸との塩であり、より好ましくは、塩酸、トリフルオロ酢酸、硝酸、硫酸、塩化テトラ−ｎ−ブチルアンモニウム又は臭化テトラ−ｎ−ブチルアンモニウムとの塩である。
In the present specification, the "salt" of the compound may be any salt as long as it forms a salt with the compound (I), and may be, for example, a Bronsted acid such as a salt with an inorganic acid or a salt with an organic acid. Salt, salt with Lewis acid and the like.
Examples of the salt with the inorganic acid include hydrochloric acid (or hydrogen chloride), nitrate, sulfuric acid, phosphoric acid, hydrobromic acid (or hydrogen bromide), hydrofluoric acid (or hydrogen fluoride), and hydrogen iodide. (Or hydrogen iodide), salts with perchloric acid and the like can be mentioned.
Examples of salts with organic acids include acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, oxalic acid, maleic acid, citric acid, fumaric acid, lactic acid, malic acid, succinic acid, tartaric acid, gluconic acid, ascorbic acid, etc. Examples thereof include salts with methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, hexafluoro-2-propanol and the like.
Examples of the salt with Lewis acid include scandium trifluoromethanesulfonate, tetra-n-butylammonium fluoride, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, and tetra-n-butylammonium iodide. , Aluminum chloride, boron trichloride, boron trifluoride, gallium chloride, tris (pentafluorophenyl) boron and the like.
The salt of compound (I) is preferably a salt in which one or two molecules of the above acid are added to one molecule of compound (I).
The salt of compound (I) is preferably hydrochloric acid, acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, nitrate, sulfuric acid, perchloric acid, hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, p. -Toluene sulfonic acid, trifluoromethanesulfonic acid, hexafluoro-2-propanol, scandium trifluoromethanesulfonate, tetra-n-butylammonium fluoride, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, iodine A salt with an acid selected from the group consisting of tetra-n-butylammonium chloride, aluminum chloride, boron trichloride, boron trifluoride, gallium chloride and boron tris (pentafluorophenyl), more preferably hydrochloric acid, A salt with trifluoroacetic acid, nitrate, sulfuric acid, tetra-n-butylammonium chloride or tetra-n-butylammonium bromide.
前記化合物（Ｉ）の塩は、非極性有機溶媒中で化合物（Ｉ）と上述した各酸とを混合することにより得られるが、両者の当量比に依らず、化合物（Ｉ）、化合物（Ｉ）に１分子の酸が付加した塩（以下、単に「一付加塩」ともいう。）及び化合物（Ｉ）に２分子の酸が付加した塩（以下、単に「二付加塩」ともいう。）の混合物が形成される。該混合物であることは、時間分解蛍光スペクトル測定及び質量分析により確認することができるが、該混合物は、平衡混合物であるため、化合物（Ｉ）、一付加塩及び二付加塩の３成分の混合比（すなわち、組成）を正確に特定することは現在の技術では不可能であるか、またはおよそ実際的ではない。そのため、本明細書及び特許請求の範囲では、本発明の蛍光組成物を、「化合物（Ｉ）と酸とを（特定の当量比で）混合してなる組成物」として特定する。また、前記化合物（Ｉ）とルイス酸（例えば、塩化テトラ−ｎ−ブチルアンモニウム又は臭化テトラ−ｎ−ブチルアンモニウム）との塩は、無溶媒で化合物（Ｉ）と酸を混合することによっても得られる。
本発明の化合物（Ｉ）の塩として、好ましくは、化合物（Ｉ）と、塩酸、酢酸、トリフルオロ酢酸、トリクロロ酢酸、プロピオン酸、硝酸、硫酸、過塩素酸、フッ化水素、塩化水素、臭化水素、ヨウ化水素、ｐ−トルエンスルホン酸、トリフルオロメタンスルホン酸、ヘキサフルオロ−２−プロパノール、トリフルオロメタンスルホン酸スカンジウム、フッ化テトラ−ｎ−ブチルアンモニウム、塩化テトラ−ｎ−ブチルアンモニウム、臭化テトラ−ｎ−ブチルアンモニウム、ヨウ化テトラ−ｎ−ブチルアンモニウム、塩化アルミニウム、三塩化ホウ素、三フッ化ホウ素、塩化ガリウム及びトリス（ペンタフルオロフェニル）ホウ素からなる群より選択される酸との一付加塩又は二付加塩であり、より好ましくは、化合物（Ｉ）と、塩酸、トリフルオロ酢酸、硝酸、硫酸、塩化テトラ−ｎ−ブチルアンモニウム又は臭化テトラ−ｎ−ブチルアンモニウムとの一付加塩又は二付加塩である。
The salt of the compound (I) can be obtained by mixing the compound (I) with each of the above-mentioned acids in a non-polar organic solvent, but the compound (I) and the compound (I) do not depend on the equivalent ratio of the two. ) With one molecule of acid (hereinafter, also simply referred to as “monoadditive salt”) and compound (I) with two molecules of acid added (hereinafter, also simply referred to as “diadded salt”). A mixture of is formed. The mixture can be confirmed by time-resolved fluorescence spectrum measurement and mass spectrometry, but since the mixture is an equilibrium mixture, it is a mixture of the three components of compound (I), monoadded salt and diadded salt. Accurate identification of ratios (ie, compositions) is not possible or nearly impractical with current technology. Therefore, in the present specification and claims, the fluorescent composition of the present invention is specified as "a composition obtained by mixing compound (I) and an acid (in a specific equivalent ratio)". The salt of the compound (I) and a Lewis acid (for example, tetra-n-butylammonium chloride or tetra-n-butylammonium bromide) can also be prepared by mixing the compound (I) and an acid without a solvent. can get.
The salt of compound (I) of the present invention is preferably compound (I), hydrochloric acid, acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, nitrate, sulfuric acid, perchloric acid, hydrogen fluoride, hydrogen chloride, and odor. Hydrochloric acid, hydrogen iodide, p-toluenesulfonic acid, trifluoromethanesulfonic acid, hexafluoro-2-propanol, scandium trifluoromethanesulfonate, tetra-n-butylammonium fluoride, tetra-n-butylammonium chloride, bromide Addition with an acid selected from the group consisting of tetra-n-butylammonium iodide, tetra-n-butylammonium iodide, aluminum chloride, boron trichloride, boron trifluoride, gallium chloride and boron tris (pentafluorophenyl). A salt or diadded salt, more preferably a monoadded salt of compound (I) with hydrochloric acid, trifluoroacetic acid, nitrate, sulfuric acid, tetra-n-butylammonium chloride or tetra-n-butylammonium bromide. It is a diadder salt.
本明細書に開示される化合物又はその塩は、溶媒和物として存在することもある。「溶媒和物」とは、本明細書に開示される化合物又はその塩に、溶媒の分子が配位したものであり、水和物も包含される。溶媒和物としては、例えば、本明細書に開示される化合物又はその塩の水和物、メタノール和物、エタノール和物、ジメチルスルホキシド和物等が挙げられる。公知の方法に従って、その溶媒和物を得ることができる。 The compounds disclosed herein or salts thereof may be present as solvates. The "solvate" is a compound or a salt thereof disclosed in the present specification in which a molecule of a solvent is coordinated, and a hydrate is also included. Examples of the solvate include hydrates of compounds or salts thereof disclosed in the present specification, methanol solvates, ethanol solvates, dimethyl sulfoxide solvates and the like. The solvate can be obtained according to a known method.
（本発明の化合物）
本発明の化合物は、下記式（Ｉ）：
(Compound of the present invention)
The compound of the present invention has the following formula (I):
[式中、
Ｒ１及びＲ１’は、それぞれ独立して、水素原子、置換されていてもよいアルキル基、置換されていてもよいシクロアルキル基又は置換されていてもよいアリール基を示し、
Ｒ２、Ｒ２’ 、Ｒ３及びＲ３’は、それぞれ独立して、水素原子又は置換されていてもよいアルキル基を示し、
ｎ個のＲは、それぞれ独立して、アルキル基を示し、並びに
ｎは、０〜４の整数を示す。]
で表される化合物又はその塩、或いはそれらの溶媒和物である。
[During the ceremony,
R 1 and R 1 'are each independently a hydrogen atom, a optionally substituted alkyl group, an optionally substituted cycloalkyl group or an optionally substituted aryl group,
R 2, R 2 ', R 3 and R 3' each independently represent a hydrogen atom or an optionally substituted alkyl group,
Each of the n Rs independently represents an alkyl group, and n represents an integer from 0 to 4. ]
It is a compound represented by, a salt thereof, or a solvate thereof.
以下、本発明の化合物（Ｉ）の各基について説明する。 Hereinafter, each group of compound (I) of the present invention will be described.
Ｒ１及びＲ１’は、それぞれ独立して、水素原子、置換されていてもよいアルキル基、置換されていてもよいシクロアルキル基又は置換されていてもよいアリール基を示す。 R 1 and R 1 'each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group or an optionally substituted aryl group.
Ｒ１及びＲ１’は、好ましくは、それぞれ独立して、アリール基又はＣ１−２０アルキル基である。 R 1 and R 1 'are preferably each independently, an aryl group or a C 1-20 alkyl group.
Ｒ１及びＲ１’は、より好ましくは、共にフェニル基又はＣ１−６アルキル基である。 R 1 and R 1 ', more preferably, are both phenyl group or a C 1-6 alkyl group.
Ｒ２、Ｒ２’ 、Ｒ３及びＲ３’は、それぞれ独立して、水素原子又は置換されていてもよいアルキル基を示す。 R 2, R 2 ', R 3 and R 3' each independently represent a hydrogen atom or an optionally substituted alkyl group.
Ｒ２、Ｒ２’ 、Ｒ３及びＲ３’は、好ましくは、それぞれ独立して、Ｃ１−６アルキル基である。 R 2, R 2 ', R 3 and R 3', preferably, each independently, a C 1-6 alkyl group.
Ｒ２、Ｒ２’ 、Ｒ３及びＲ３’は、より好ましくは、共にＣ１−４アルキル基である。 R 2, R 2 ', R 3 and R 3', and more preferably, are both C 1-4 alkyl groups.
ｎ個のＲは、それぞれ独立して、アルキル基を示す。 The n R's each independently represent an alkyl group.
ｎ個のＲは、好ましくは、それぞれ独立して、Ｃ１−６アルキル基である。 The n R's are preferably C 1-6 alkyl groups, each independently.
ｎ個のＲは、より好ましくは、それぞれ独立して、Ｃ１−４アルキル基である。 The n R's are more preferably C 1-4 alkyl groups, each independently.
ｎは、０〜４の整数を示す。 n represents an integer from 0 to 4.
ｎは、好ましくは、０である。 n is preferably 0.
化合物（Ｉ）としては、以下の化合物が好適である。 As the compound (I), the following compounds are suitable.
［化合物（ＩＡ）］
Ｒ１及びＲ１’が、それぞれ独立して、アリール基又はＣ１−２０アルキル基であり、Ｒ２、Ｒ２’ 、Ｒ３及びＲ３’が、それぞれ独立して、Ｃ１−６アルキル基であり、且つｎが０である、化合物（Ｉ）。
[Compound (IA)]
R 1 and R 1 'are each independently, an aryl group or a C 1-20 alkyl group, R 2, R 2', R 3 is and R 3 'each, independently, C 1-6 alkyl Compound (I) which is a group and n is 0.
［化合物（ＩＢ）］
Ｒ１及びＲ１’が、共にフェニル基又はＣ１−６アルキル基であり、Ｒ２、Ｒ２’ 、Ｒ３及びＲ３’が、共にＣ１−４アルキル基であり、且つｎが０である、化合物（Ｉ）。
[Compound (IB)]
R 1 and R 1 'are both phenyl group or a C 1-6 alkyl group, R 2, R 2', R 3 is and R 3 'are both C 1-4 alkyl group, and n is 0 Compound (I).
［化合物（ＩＣ）］
Ｒ１及びＲ１’が、共にフェニル基又はＣ１−６アルキル基であり、Ｒ２、Ｒ２’ 、Ｒ３及びＲ３’が、共にＣ１−４アルキル基であり、Ｒが、それぞれ独立して、Ｃ１−４アルキル基であり、且つｎが１〜４である、化合物（Ｉ）。
[Compound (IC)]
R 1 and R 1 'are both phenyl group or a C 1-6 alkyl group, R 2, R 2', R 3 is and R 3 'are both C 1-4 alkyl radical, R is, respectively Independently, compound (I) is a C 1-4 alkyl group and n is 1-4.
特に好適な化合物（Ｉ）は、具体的には、下記式（Ｉａ）： A particularly suitable compound (I) is specifically described in the following formula (Ia):
で表される化合物、又は下記式（Ｉｂ）： The compound represented by, or the following formula (Ib):
で表される化合物である。 It is a compound represented by.
本発明による化合物（Ｉ）が不斉中心を有する場合、エナンチオマーあるいはジアステレオマーなどの異性体が存在しうる。このような異性体及びそれらの混合物はすべて本発明の範囲内に包含される。また、コンホメーションあるいは互変異性による異性体が生成する場合があるが、このような異性体あるいはその混合物も本発明の化合物（Ｉ）に含まれる。 When compound (I) according to the present invention has an asymmetric center, isomers such as enantiomers or diastereomers may be present. All such isomers and mixtures thereof are included within the scope of the present invention. In addition, isomers may be produced by conformation or tautomerism, and such isomers or mixtures thereof are also included in the compound (I) of the present invention.
（本発明の化合物（Ｉ）の合成）
本発明の化合物（Ｉ）の製造方法について以下に説明する。
(Synthesis of compound (I) of the present invention)
The method for producing the compound (I) of the present invention will be described below.
以下の製造方法における各工程では反応液のままか、または粗生成物として得た後に、次反応に用いることもできる、あるいは、各工程で得られた化合物を、常法に従って、反応混合物から濃縮、晶出、再結晶、蒸留、溶媒抽出、分溜、クロマトグラフィーなどの分離手段により単離及び／又は精製することができる。 In each step of the following production method, the reaction solution can be used as it is or as a crude product and then used in the next reaction, or the compound obtained in each step is concentrated from the reaction mixture according to a conventional method. , Crystallization, recrystallization, distillation, solvent extraction, distillation, chromatography and the like can be isolated and / or purified.
本発明の化合物（Ｉ）の製造方法としては、特に限定されないが、例えば、下記の反応式で示される方法またはそれに準じた方法等により製造することができる。
反応式
The method for producing the compound (I) of the present invention is not particularly limited, but for example, it can be produced by a method represented by the following reaction formula or a method similar thereto.
Reaction equation
［式中の各記号は、前記と同義である。］ [Each symbol in the formula has the same meaning as described above. ]
（工程１）
本工程は、自体公知の方法（例えば、Setsune, J. et al., Tetrahedron Lett., 2006, 47, 7541-7544.参照）又はそれに準ずる方法に従って製造される化合物（１）を、塩基存在下、加熱還流することにより、化合物（２）を製造する工程である。
使用する塩基としては、例えば、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物が好適に用いられる。
塩基の使用量は、化合物（１）１当量に対して、通常、２〜２０当量、好ましくは４〜１０当量、特に好ましくは８〜１０当量である。
この反応は、反応に影響を及ぼさない高沸点の溶媒中で行うのが好ましい。このような溶媒としては、例えば、芳香族炭化水素類（例、キシレン、メシチレン等）、アルコール類（例、エチレングリコール等）、ニトリル類（例、ベンゾニトリル等）、エーテル類（例、ジグリム等）等が挙げられるが、中でも、エチレングリコールが好ましい。
この反応は、加熱還流下（通常約１００〜２２０℃、好ましくは約１３０〜２００℃）で行うことができる。
反応時間は、通常１〜３０時間、好ましくは１〜２０時間、さらに好ましくは２〜１０時間である。
(Step 1)
In this step, compound (1) produced according to a method known per se (see, for example, Setsune, J. et al., Tetrahedron Lett., 2006, 47, 7541-7544.) Or a method similar thereto is subjected to the presence of a base. , A step of producing compound (2) by heating and refluxing.
As the base to be used, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferably used.
The amount of the base used is usually 2 to 20 equivalents, preferably 4 to 10 equivalents, and particularly preferably 8 to 10 equivalents, relative to 1 equivalent of compound (1).
This reaction is preferably carried out in a solvent having a high boiling point that does not affect the reaction. Examples of such a solvent include aromatic hydrocarbons (eg, xylene, mesitylene, etc.), alcohols (eg, ethylene glycol, etc.), nitriles (eg, benzonitrile, etc.), ethers (eg, diglyme, etc.). ), Etc., but among them, ethylene glycol is preferable.
This reaction can be carried out under heating and reflux (usually about 100-220 ° C, preferably about 130-200 ° C).
The reaction time is usually 1 to 30 hours, preferably 1 to 20 hours, and more preferably 2 to 10 hours.
（工程２）
本工程は、化合物（２）を、自体公知のホルミル化反応（Vilsmeier-Haack反応）に付すことにより、化合物（３）を製造する工程である。
この反応に用いるホルミル化剤（Vilsmeier試薬）としては、例えば、塩化ホスホリルとＮ，Ｎ−ジメチルホルムアミドが好適に用いられる。
ホルミル化剤の使用量は、化合物（２）１当量に対して、通常、２〜２０当量、好ましくは４〜１０当量である。
この反応は、反応に影響を及ぼさない溶媒中で行うのが好ましい。このような溶媒としては、例えば、ハロゲン化炭化水素類（例、ジクロロメタン、１，２−ジクロロエタン等）、芳香族炭化水素類（例、ベンゼン、トルエン等）、アルコール類、エーテル類、アセトン、アセトニトリル、酢酸エチル、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、1-メチル-2-ピロリドン、ジメチルスルホキシド、ヘキサメチルホスホルアミドまたはこれらの混合溶媒が挙げられるが、中でも、１，２−ジクロロエタンが好ましい。
この反応は、冷却下（通常約−７８〜２０℃、好ましくは約−１０〜１０℃）、室温下または加熱下（通常約４０〜２００℃、好ましくは約４０〜１６０℃）に行うことができる。
反応時間は、通常１〜３０時間、好ましくは１〜２０時間、さらに好ましくは１〜１０時間である。
(Step 2)
This step is a step of producing compound (3) by subjecting compound (2) to a formylation reaction (Vilsmeier-Haack reaction) known per se.
As the formylation agent (Vilsmeier reagent) used in this reaction, for example, phosphoryl chloride and N, N-dimethylformamide are preferably used.
The amount of the formylating agent used is generally 2 to 20 equivalents, preferably 4 to 10 equivalents, relative to 1 equivalent of compound (2).
This reaction is preferably carried out in a solvent that does not affect the reaction. Examples of such a solvent include halogenated hydrocarbons (eg, dichloromethane, 1,2-dichloroethane, etc.), aromatic hydrocarbons (eg, benzene, toluene, etc.), alcohols, ethers, acetone, acetonitrile. , Ethyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide or a mixed solvent thereof. Among them, 1,2- Dichloroethane is preferred.
This reaction can be carried out under cooling (usually about −78 to 20 ° C., preferably about −10 to 10 ° C.), at room temperature or under heating (usually about 40 to 200 ° C., preferably about 40 to 160 ° C.). it can.
The reaction time is usually 1 to 30 hours, preferably 1 to 20 hours, and more preferably 1 to 10 hours.
（工程３）
本工程は、化合物（３）を、式：
(Step 3)
In this step, compound (3) is expressed in formula:
（式中、Ｒ１は、前記と同義である。）
で表されるアミンと反応させることにより、化合物（Ｉ）を製造する工程である。当該反応は、必要に応じて酸触媒の存在下で、反応に影響を及ぼさない溶媒中で行われる。
(In the formula, R 1 is synonymous with the above.)
This is a step of producing compound (I) by reacting with an amine represented by. The reaction is carried out in the presence of an acid catalyst, if necessary, in a solvent that does not affect the reaction.
酸触媒としては、例えば、トリフルオロ酢酸、トリクロロ酢酸、トリフルオロメタンスルホン酸、塩酸等が挙げられるが、中でもトリフルオロ酢酸が特に好ましい。
酸触媒の使用量は、使用する酸の種類により異なるが、化合物（３）１当量に対して、通常、０．１〜１０当量、好ましくは０．５当量である。
この反応は、反応に影響を及ぼさない溶媒中で行うのが好ましい。このような溶媒としては、例えば、ハロゲン化炭化水素類（例、ジクロロメタン、クロロホルム、１，２−ジクロロエタン等）、芳香族炭化水素類（例、ベンゼン、トルエン等）、炭化水素類（例、ヘキサン等）、水等が挙げられるが、中でも、ジクロロメタン又は水が好ましい。
この反応は、通常約０℃〜室温下で行うことができる。
反応時間は、通常１〜３０時間、好ましくは１〜２０時間、さらに好ましくは１〜１０時間である。
Examples of the acid catalyst include trifluoroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, hydrochloric acid and the like, and trifluoroacetic acid is particularly preferable.
The amount of the acid catalyst used varies depending on the type of acid used, but is usually 0.1 to 10 equivalents, preferably 0.5 equivalents, relative to 1 equivalent of compound (3).
This reaction is preferably carried out in a solvent that does not affect the reaction. Examples of such a solvent include halogenated hydrocarbons (eg, dichloromethane, chloroform, 1,2-dichloroethane, etc.), aromatic hydrocarbons (eg, benzene, toluene, etc.), and hydrocarbons (eg, hexane). Etc.), water and the like, but dichloromethane or water is preferable.
This reaction can usually be carried out at about 0 ° C. to room temperature.
The reaction time is usually 1 to 30 hours, preferably 1 to 20 hours, and more preferably 1 to 10 hours.
（本発明の化合物（Ｉ）と酸とを混合してなる蛍光組成物）
本発明の化合物（Ｉ）は、非極性有機溶媒中か、又は無溶媒下で酸を添加することにより蛍光発光させることが可能である。また、化合物（Ｉ）に対する酸の当量比を変化させることにより、単一分子でありながら異なる蛍光色を発現させることが可能である。特に、後述する実験例１において示されるように、本発明の化合物（Ｉ）と酸とを特定の当量比で混合してなる組成物は、通常、単一分子では発現させることが難しい白色蛍光を発することができる点で有用である。当該蛍光組成物について、以下に説明する。
(Fluorescent composition obtained by mixing compound (I) of the present invention and an acid)
The compound (I) of the present invention can be fluorescently emitted by adding an acid in a non-polar organic solvent or in the absence of a solvent. Further, by changing the equivalent ratio of the acid to the compound (I), it is possible to express different fluorescent colors even though it is a single molecule. In particular, as shown in Experimental Example 1 described later, a composition obtained by mixing the compound (I) of the present invention and an acid at a specific equivalent ratio is usually white fluorescence that is difficult to express with a single molecule. It is useful in that it can emit. The fluorescent composition will be described below.
本発明の化合物（Ｉ）は、非極性有機溶媒（例、ジクロロメタン、クロロホルム、テトラヒドロフラン）中で青色蛍光を発する化合物である。化合物（Ｉ）（例、化合物（Ｉａ））に対し、０．７〜１．０当量のブレンステッド酸（例、トリフルオロ酢酸）を添加すると、下記式： Compound (I) of the present invention is a compound that emits blue fluorescence in a non-polar organic solvent (eg, dichloromethane, chloroform, tetrahydrofuran). When 0.7 to 1.0 equivalent of Bronsted acid (eg, trifluoroacetic acid) is added to compound (I) (eg, compound (Ia)), the following formula:
で表される化合物（Ｉａ）、化合物（Ｉａ）の一付加塩（化合物（Ｉａ−１））、及び化合物（Ｉａ）の二付加塩（化合物（Ｉａ−２））の混合物が形成され、白色蛍光を発する。これらは平衡混合物であるため、組成比を正確に特定することは困難であるが、３種の混合物の状態で存在していることは、時間分解蛍光スペクトル測定及び質量分析により確認することができる。 A mixture of compound (Ia) represented by (Ia), a monoadded salt of compound (Ia) (compound (Ia-1)), and a diadded salt of compound (Ia) (compound (Ia-2)) is formed and is white. It emits fluorescence. Since these are equilibrium mixtures, it is difficult to accurately specify the composition ratio, but the existence of the three mixtures can be confirmed by time-resolved fluorescence spectrum measurement and mass spectrometry. ..
化合物（Ｉａ−１）は、単独では、赤色蛍光を示し、化合物（Ｉａ−２）は、単独では、緑色蛍光を示すことが時間分解蛍光スペクトルにより確認されたことから、ブレンステッド酸の添加により、青、赤及び緑色の各成分が絶妙なバランスで形成され、紫外線（波長１０〜４００ｎｍ）を吸収することにより、国際照明委員会（ＣＩＥ：Commission Internationale de l'Eclairage）（１９３１）色度図における色度座標（ｘ，ｙ）、（０．３２〜０．３４，０．３２〜０．３４）を示す白色蛍光を発すると推定される。また、同様の蛍光発光特性は、ルイス酸の添加によっても発現させることが可能である。具体的には、後述する実験例１に記載のように、ルイス酸として、塩化テトラ−ｎ−ブチルアンモニウムを、化合物（Ｉａ）に対し、５００当量添加すると、ブレンステッド酸添加時と同様の紫外−可視吸収スペクトル及び発光スペクトルを示し、白色蛍光が確認された。
このことから、化合物（Ｉ）と酸を混合してなる組成物において、白色蛍光発現に必要な酸の当量は、添加する酸の種類により変化し、その変化は、化合物（Ｉ）との塩形成のされ易さに起因すると推定することができる。
Since it was confirmed by the time-resolved fluorescence spectrum that the compound (Ia-1) exhibited red fluorescence alone and the compound (Ia-2) exhibited green fluorescence alone, it was confirmed by the addition of blended acid. , Blue, red and green components are formed in an exquisite balance and absorb ultraviolet rays (wavelength 10 to 400 nm), thereby chromaticity diagram of the Commission Internationale de l'Eclairage (CIE) (1931). It is presumed to emit white fluorescence indicating the chromaticity coordinates (x, y) in (0.32-0.34, 0.32-0.34). Further, the same fluorescence emission characteristics can be exhibited by adding Lewis acid. Specifically, as described in Experimental Example 1 described later, when 500 equivalents of tetra-n-butylammonium chloride as Lewis acid is added to compound (Ia), the same ultraviolet rays as when Bronsted acid is added. -Visible absorption spectrum and emission spectrum were shown, and white fluorescence was confirmed.
From this, in the composition obtained by mixing the compound (I) and the acid, the equivalent amount of the acid required for the expression of white fluorescence changes depending on the type of the acid to be added, and the change is the salt with the compound (I). It can be presumed that it is due to the ease of formation.
一方、本発明の化合物（Ｉ）と化学構造上、類似するが、化合物（Ｉ）の範囲外である下記式： On the other hand, the following formula: which is similar in chemical structure to compound (I) of the present invention but is outside the range of compound (I):
で表される化合物それぞれについて、酸（トリフルオロ酢酸）の添加による蛍光発光特性を、添加する酸の当量比を変えて調べた結果、酸の当量の多少に関わらず、いずれの場合にも白色蛍光を発現させることはできなかった。
以上より、白色蛍光を発現させるためには、芳香環で架橋されたビピロール骨格を有することに加えて、以下の構造上の特徴を具備する必要がある。すなわち、（１）ピロールに結合する２個のイミン構造、（２）該イミンに隣接するメチレン基、及び（３）架橋芳香環が、１，４−フェニレンである、化合物、すなわち、本発明の化合物（Ｉ）、であることが必要である。
As a result of examining the fluorescence emission characteristics of each of the compounds represented by (3) by changing the equivalent ratio of the acid to be added, the fluorescence emission characteristics due to the addition of the acid (trifluoroacetic acid) were examined. Fluorescence could not be expressed.
From the above, in order to express white fluorescence, it is necessary to have the following structural features in addition to having a bipyrol skeleton crosslinked with an aromatic ring. That is, a compound in which (1) two imine structures bonded to pyrrole, (2) a methylene group adjacent to the imine, and (3) a crosslinked aromatic ring are 1,4-phenylene, that is, the present invention. It is necessary to be compound (I).
本発明の化合物（Ｉ）と酸を混合してなる蛍光組成物は、化合物（Ｉ）と酸以外に、各種非極性有機溶媒、その蛍光発光特性に悪影響を及ぼさない添加剤等を更に含有していてもよい。 The fluorescent composition obtained by mixing the compound (I) of the present invention and an acid further contains various non-polar organic solvents, additives that do not adversely affect the fluorescence emission characteristics thereof, and the like, in addition to the compound (I) and the acid. May be.
本発明の化合物（Ｉ）と酸を混合してなる蛍光組成物は、単一分子で、酸を添加するだけという簡便な操作により、発光量子収率が高く、質の高い白色蛍光を発することができ、また、化合物としての安定性（すなわち、耐久性）も高いことから、蛍光発光素子として有用である。 The fluorescent composition obtained by mixing the compound (I) of the present invention and an acid is a single molecule and emits high-quality white fluorescence with a high emission quantum yield by a simple operation of simply adding an acid. It is also useful as a fluorescent light emitting element because of its high stability (that is, durability) as a compound.
以下に実施例及び実験例を挙げて、本発明を更に具体的に説明するが、これによって本発明が限定されるものではなく、また本発明の範囲を逸脱しない範囲で変化させてもよい。
反応は、Ｍｅｒｃｋ ６０ Ｆ２５４ シリカゲルプレート（厚さ０．２５ｍｍ）を用いて、薄層クロマトグラフィーによりモニターした。
１Ｈ及び１３Ｃ−ＮＭＲスペクトルは、Ｂｒｕｋｅｒ ＡＶＡＮＣＥ ４００を用い、内部標準として、テトラメチルシランを用いて、重クロロホルム又は重ジメチルスルホキシドを溶媒として測定した。１Ｈ−ＮＭＲについてのデータは、化学シフト（δｐｐｍ）、多重度（ｓ＝シングレット、ｄ＝ダブレット、ｔ＝トリプレット、ｑ＝カルテット、ｍ＝マルチプレット、ｂｒ＝ブロード）、カップリング定数（Ｈｚ）、積分及び割当てとして報告する。
吸収スペクトルは、ＪＡＳＣＯ ＥＴＣ−７１７温度／撹拌調節器を装着したＪＡＳＣＯ Ｖ−６７０ ＵＶ／ＶＩＳ／ＮＩＲを用いて測定した。発光スペクトルは、ＪＡＳＣＯ ＥＴＣ−２７３Ｔ温度／撹拌調節器を装着したＪＡＳＣＯ ＦＰ−６５００を用いて測定した。フーリエ変換赤外スペクトルは、ＪＳＣＯ ＦＴ／ＩＲ ４２００を用いて測定した。フーリエ変換質量分析は、Ｔｈｅｒｍｏ Ｆｉｓｈｅｒ Ｓｃｉｅｎｔｉｆｉｃ ＬＴＱ Ｏｒｂｉｔｒａｐを用いて測定した。
以下の実施例中の「室温」は通常約１０℃ないし約３０℃を示す。％は、収率についてはｍｏｌ／ｍｏｌ％を、その他については特に断らない限り重量％を示す。
Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples, but the present invention is not limited thereto, and may be changed without departing from the scope of the present invention.
The reaction was monitored by thin layer chromatography using a Merck 60 F254 silica gel plate (thickness 0.25 mm).
1 H and 13 C-NMR spectra were measured using Bruker AVANCE 400, tetramethylsilane as an internal standard, and deuterated chloroform or deuterated dimethylsulfoxide as a solvent. The data for 1 1 H-NMR are chemical shift (δppm), multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, br = broad), coupling constant (Hz). , Integral and allocation.
The absorption spectrum was measured using JASCO V-670 UV / VIS / NIR equipped with a JASCO ETC-717 temperature / stirring controller. The emission spectrum was measured using a JASCO FP-6500 equipped with a JASCO ETC-273T temperature / stirring controller. The Fourier transform infrared spectrum was measured using JSCO FT / IR 4200. The Fourier transform mass spectrometry was measured using the Thermo Fisher Scientific LTQ Orbitrap.
"Room temperature" in the following examples usually indicates about 10 ° C to about 30 ° C. % Indicates mol / mol% for yield and% by weight for others unless otherwise specified.
以下の実施例において、化合物（Ｉａ）、化合物（Ｉｂ）、化合物（ＩＩａ）、化合物（ＩＩｂ）、化合物（ＩＩｃ）又は化合物（ＩＩｄ）の合成に使用した原料化合物は、自体公知の方法（例えば、Setsune, J. et al., Tetrahedron Lett., 2006, 47, 7541-7544.参照）、又はそれに準ずる方法に従って製造することができる。また、当該原料化合物の合成に用いる１，４−ジヨードベンゼン（東京化成工業株式会社製）、１，３−ジヨードベンゼン（東京化成工業株式会社製）、２，５−ジヨードチオフェン（Ｓｉｇｍａ−Ａｌｄｒｉｃｈ社製）、アニリン（ナカライテスク社製）、ベンジルアミン（ナカライテスク社製）及びｎ−ヘキシルアミン（ナカライテスク社製）は、市販品をそのまま使用した。その他の原料化合物は、市販品をそのまま使用するか、又は自体公知の方法若しくはそれに準ずる方法に従って製造することができる。
メタノール、エタノール及びジクロロメタンは、試薬グレードのものを購入し、そのまま用いた。その他の試薬は、市販品をそのまま使用するか、又は必要に応じて精製してから用いた。
In the following examples, the starting compound used for the synthesis of compound (Ia), compound (Ib), compound (IIa), compound (IIb), compound (IIc) or compound (IId) is a method known per se (eg, for example. , Setsune, J. et al., Tetrahedron Lett., 2006, 47, 7541-7544.), Or a similar method. In addition, 1,4-diiodobenzene (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 1,3-diiodobenzene (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 2,5-diiodothiophene (Sigma) used for the synthesis of the raw material compound. -For Aldrich), aniline (manufactured by Nacalai Tesque), benzylamine (manufactured by Nacalai Tesque) and n-hexylamine (manufactured by Nacalai Tesque), commercially available products were used as they were. Other raw material compounds can be produced by using commercially available products as they are, or by a method known per se or a method similar thereto.
As for methanol, ethanol and dichloromethane, reagent grades were purchased and used as they were. For other reagents, commercially available products were used as they were, or purified as necessary before use.
実施例１
（Ｎ，Ｎ’Ｅ，Ｎ，Ｎ’Ｅ）−Ｎ，Ｎ’−（（５，５’−（１，４−フェニレン）ビス（３，４−ジエチル−１Ｈ−ピロール−５，２−ジイル））ビス（メタニリリデン））ビス（１−フェニルメタンアミン） （化合物（Ｉａ））の合成
Example 1
(N, N'E, N, N'E) -N, N'-((5,5'-(1,4-phenylene) bis (3,4-diethyl-1H-pyrrole-5,2-diyl) )) Synthesis of bis (methanilylidene)) bis (1-phenylmethaneamine) (compound (Ia))
（工程１）
１，４−ビス（３，４−ジエチル−１Ｈ−ピロール−２−イル）ベンゼン（２ａ）の合成
２００ｍｌナスフラスコにジエチル ５，５’−（１，４−フェニレン）ビス（３，４−ジエチル−１Ｈ−ピロール−２−カルボキシレート）（１ａ）（２．７ｇ，５．８１ｍｍｏｌ）、水酸化ナトリウム（１．４ｇ，３５ｍｍｏｌ）及びエチレングリコール（８２ｍＬ）を加え、アルゴン置換した。該混合物を、撹拌しながら２時間３０分間、加熱還流した。その後、反応混合物を室温まで放冷すると針状結晶が析出した。氷冷後、反応混合物に冷水を加えてグラスフィルターで吸引ろ過し、水で洗浄することにより標題化合物（２ａ）（１．６ｇ，収率：８６％）を黄色結晶として得た。
(Step 1)
Synthesis of 1,4-bis (3,4-diethyl-1H-pyrrole-2-yl) benzene (2a) Diethyl 5,5'-(1,4-phenylene) bis (3,4-diethyl) in a 200 ml eggplant flask -1H-pyrrole-2-carboxylate) (1a) (2.7 g, 5.81 mmol), sodium hydroxide (1.4 g, 35 mmol) and ethylene glycol (82 mL) were added and replaced with argon. The mixture was heated to reflux with stirring for 2 hours and 30 minutes. Then, when the reaction mixture was allowed to cool to room temperature, acicular crystals were precipitated. After cooling with ice, cold water was added to the reaction mixture, suction filtration was performed with a glass filter, and the mixture was washed with water to obtain the title compound (2a) (1.6 g, yield: 86%) as yellow crystals.
（工程２）
５，５’−（１，４−フェニレン）ビス（３，４−ジエチル−１Ｈ−ピロール−２−カルボアルデヒド）（３ａ）の合成
５０ｍＬ二口ナスフラスコをアルゴン置換し、０℃でＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）（２．７ｍＬ，３４．９ｍｍｏｌ）及び塩化ホスホリル（３．２ｍＬ，３４．２ｍｍｏｌ）を加え、室温で３０分間撹拌し、Vilsmeier試薬を調製した。別の５０ｍＬ二口フラスコに、１，４−ビス（３，４−ジエチル−１Ｈ−ピロール−２−イル）ベンゼン（２ａ）（１．１ｇ，３．４３ｍｍｏｌ）を加え、アルゴン置換後、２０ｍＬの１，２−ジクロロエタンを加えて、０℃に冷却した。調製したVilsmeier試薬を１０ｍＬの１，２−ジクロロエタンに溶かし、化合物（２ａ）の溶液にゆっくりとシリンジで滴下した。その後、反応液を室温で終夜撹拌した。反応液を０℃に冷却し、炭酸カリウム水溶液（１２ｇ／２０ｍＬ）を加えた後、８０℃に加熱して２時間撹拌した。反応混合物をジクロロメタンで抽出し、無水硫酸ナトリウムで乾燥させた。溶媒を減圧留去し、ジクロロメタンとメタノールを添加することにより再沈殿させることで、標題化合物（３ａ）（１．２ｇ，収率：９３％）を茶色固体として得た。
1H NMR (400 MHz, CDCl3, 20℃):δ 9.65 (s, 2H, CHO), 9.53 (br., 2H, NH), 7.58 (s, 4H, phenylene-H), 2.81 (q, J = 7.6 Hz, 4H, CH2), 2.64 (q, J = 7.6 Hz, 4H, CH2), 1.29 (t, J = 7.6 Hz, 6H, CH3), 1.20 (t, J = 7.6 Hz, 6H, CH3);
13C NMR (100 MHz, CDCl3, 20℃):δ 177.23, 138.90, 136.02, 131.56, 128.74, 127.79, 124.90, 17.75, 17.32, 17.13, 15.92;
IR (ATR): 3300, 3264, 3054, 2965, 2924, 2872, 2809, 2361, 1629, 1442, 1384, 1337, 1287, 1265, 1237, 1197, 1090, 892, 735, 704, 629, 588 cm-1; Anal. Calcd for C24H28N2O2: C, 76.56; H, 7.50; N, 7.29 Found: C, 75.89; H, 7.14; N, 7.29.
(Step 2)
Synthesis of 5,5'-(1,4-phenylene) bis (3,4-diethyl-1H-pyrrole-2-carbaldehyde) (3a)
A 50 mL two-necked eggplant flask is replaced with argon, N, N-dimethylformamide (DMF) (2.7 mL, 34.9 mmol) and phosphoryl chloride (3.2 mL, 34.2 mmol) are added at 0 ° C., and 30 minutes at room temperature. Stirred to prepare Vilsmeier reagent. To another 50 mL two-necked flask, add 1,4-bis (3,4-diethyl-1H-pyrrole-2-yl) benzene (2a) (1.1 g, 3.43 mmol), and after argon substitution, add 20 mL. 1,2-Dichloroethane was added and cooled to 0 ° C. The prepared Vilsmeier reagent was dissolved in 10 mL of 1,2-dichloroethane and slowly added dropwise to the solution of compound (2a) with a syringe. Then, the reaction solution was stirred at room temperature overnight. The reaction mixture was cooled to 0 ° C., an aqueous potassium carbonate solution (12 g / 20 mL) was added, and the mixture was heated to 80 ° C. and stirred for 2 hours. The reaction mixture was extracted with dichloromethane and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure and reprecipitated by adding dichloromethane and methanol to give the title compound (3a) (1.2 g, yield: 93%) as a brown solid.
1 1 H NMR (400 MHz, CDCl 3 , 20 ° C): δ 9.65 (s, 2H, CHO), 9.53 (br., 2H, NH), 7.58 (s, 4H, phenylene-H), 2.81 (q, J = 7.6 Hz, 4H, CH 2 ), 2.64 (q, J = 7.6 Hz, 4H, CH 2 ), 1.29 (t, J = 7.6 Hz, 6H, CH 3 ), 1.20 (t, J = 7.6 Hz, 6H , CH 3 );
13 C NMR (100 MHz, CDCl 3 , 20 ° C): δ 177.23, 138.90, 136.02, 131.56, 128.74, 127.79, 124.90, 17.75, 17.32, 17.13, 15.92;
IR (ATR): 3300, 3264 , 3054, 2965, 2924, 2872, 2809, 2361, 1629, 1442, 1384, 1337, 1287, 1265, 1237, 1197, 1090, 892, 735, 704, 629, 588 cm - 1 ; Anal. Calcd for C 24 H 28 N 2 O 2 : C, 76.56; H, 7.50; N, 7.29 Found: C, 75.89; H, 7.14; N, 7.29.
（工程３）
（Ｎ，Ｎ’Ｅ，Ｎ，Ｎ’Ｅ）−Ｎ，Ｎ’−（（５，５’−（１，４−フェニレン）ビス（３，４−ジエチル−１Ｈ−ピロール−５，２−ジイル））ビス（メタニリリデン））ビス（１−フェニルメタンアミン）（Ｉａ）の合成
試験管に化合物（３ａ）（５０ｍｇ，０．１３ｍｍｏｌ）、ベンジルアミン（０．３ｍＬ，２．７５ｍｍｏｌ）、メタノール（５ｍＬ）、ジクロロメタン（０．１ｍＬ）及びトリフルオロ酢酸（２滴）を加えて、室温で終夜撹拌した。反応溶液に炭酸カリウムを加え、ジクロロメタンで抽出し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を減圧留去し、残渣にジクロロメタンとメタノールを加えることにより再沈殿させることで、標題化合物（Ｉａ）（３９ｍｇ，収率：５３％）を黄色固体として得た。
1H NMR (400 MHz, CDCl3, 20℃): δ 8.29 (s, 2H, CH=N), 7.51 (s, 4H, phenylene-H), 7.38-7.26 (m, 10H, phenyl-H), 4.76 (s, 4H, benzyl-H), 2.69 (q, J = 7.6 Hz, 4H, CH2), 2.66 (q, J = 7.6 Hz, 4H, CH2), 1.26 (t, J = 7.6 Hz, 6H, CH3), 1.23 (t, J = 7.6 Hz, 6H, CH3);
13C NMR (100 MHz, CDCl3, 20℃): δ 150.55, 139.92, 131.63, 131.59, 131.404, 128.45, 127.85, 127.10, 126.88, 125.86, 123.43, 64.76, 17.60, 17.53, 17.11, 16.15;
IR (ATR): 2978, 2921, 2791, 2362, 1624, 1470, 1434, 1383, 1291, 1236, 735, 630, 558 cm-1;
HRMS: m/z calculated for [M+H]+(C38H42N4) 555.3487, found 555.3497.
(Step 3)
(N, N'E, N, N'E) -N, N'-((5,5'-(1,4-phenylene) bis (3,4-diethyl-1H-pyrrole-5,2-diyl) )) Synthesis of bis (methanilylidene)) bis (1-phenylmethaneamine) (Ia) Compound (3a) (50 mg, 0.13 mmol), benzylamine (0.3 mL, 2.75 mmol), methanol (5 mL) in a test tube. ), dichloromethane (0.1 mL) and trifluoroacetic acid (2 drops) were added, and the mixture was stirred overnight at room temperature. Potassium carbonate was added to the reaction solution, the mixture was extracted with dichloromethane, and the organic layer was dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure and reprecipitation was carried out by adding dichloromethane and methanol to the residue to give the title compound (Ia) (39 mg, yield: 53%) as a yellow solid.
1 1 H NMR (400 MHz, CDCl 3 , 20 ° C): δ 8.29 (s, 2H, CH = N), 7.51 (s, 4H, phenylene-H), 7.38-7.26 (m, 10H, phenyl-H), 4.76 (s, 4H, benzyl-H), 2.69 (q, J = 7.6 Hz, 4H, CH 2 ), 2.66 (q, J = 7.6 Hz, 4H, CH 2 ), 1.26 (t, J = 7.6 Hz, 6H, CH 3 ), 1.23 (t, J = 7.6 Hz, 6H, CH 3 );
13 C NMR (100 MHz, CDCl 3 , 20 ° C): δ 150.55, 139.92, 131.63, 131.59, 131.404, 128.45, 127.85, 127.10, 126.88, 125.86, 123.43, 64.76, 17.60, 17.53, 17.11, 16.15;
IR (ATR): 2978, 2921, 2791, 2362, 1624, 1470, 1434, 1383, 1291, 1236, 735, 630, 558 cm -1 ;
HRMS: m / z calculated for [M + H] + (C 38 H 42 N 4 ) 555.3487, found 555.3497.
実施例２
（Ｎ，Ｎ’Ｅ，Ｎ，Ｎ’Ｅ）−Ｎ，Ｎ’−（（５，５’−（１，４−フェニレン）ビス（３，４−ジエチル−１Ｈ−ピロール−５，２−ジイル））ビス（メタニリリデン））ビス（１−ヘキサンアミン） （化合物（Ｉｂ））の合成
Example 2
(N, N'E, N, N'E) -N, N'-((5,5'-(1,4-phenylene) bis (3,4-diethyl-1H-pyrrole-5,2-diyl) )) Synthesis of bis (methanilylidene)) bis (1-hexaneamine) (compound (Ib))
試験管に化合物（３ａ）（１００ｍｇ，０．２７ｍｍｏｌ）、ｎ−ヘキシルアミン（０．３ｍＬ，２．２７ｍｍｏｌ）及び水（５ｍＬ）を加え、室温で終夜撹拌した。沈殿物をろ別し、乾燥させた後、ｎ−ヘキサンで洗浄して、標題化合物（Ｉｂ）（１００ｍｇ，収率：６９％）を肌色固体として得た。
1H NMR (400 MHz, CDCl3, 20℃): δ 8.15 (s, 2H, imine-H), 7.51 (s, 4H, phenylene-H), 6.70 (br., 2H, NH), 3.51 (t, J = 7.2 Hz, 4H, hexyl-CH2), 2.68 (q, J = 7.2 Hz, 4H, CH2), 2.66 (q, J = 7.2 Hz, 4H, CH2), 1.67-1.60 (m, 4H, hexyl), 1.41-1.29 (m, 12H, hexyl), 1.25 (t, J = 7.2 Hz, 6H, CH3), 1.23 (t, J = 7.2 Hz, 6H, CH3), 0.91 (t, J = 7.2 Hz, 6H, hexyl-CH3);
13C NMR (100 MHz, CDCl3, 20℃): δ 149.55, 131.55, 131.22, 130.96, 127.16, 126.06, 123.41, 61.56, 31.87, 31.53, 27.16, 22.82, 17.75, 17.62, 17.19, 16.31, 14.26;
IR (ATR): 2979, 2920, 2791, 2020, 1623, 1470, 1433, 1383, 1273, 1236, 1090, 888, 735, 703, 631, 572, 562 cm-1;
HRMS: m/z calculated for [M+H]+ (C36H54N4) 543.4426, found 543.4423.
Compound (3a) (100 mg, 0.27 mmol), n-hexylamine (0.3 mL, 2.27 mmol) and water (5 mL) were added to a test tube, and the mixture was stirred overnight at room temperature. The precipitate was filtered off, dried and then washed with n-hexane to give the title compound (Ib) (100 mg, yield: 69%) as a flesh-colored solid.
1 1 H NMR (400 MHz, CDCl 3 , 20 ° C): δ 8.15 (s, 2H, imine-H), 7.51 (s, 4H, phenylene-H), 6.70 (br., 2H, NH), 3.51 (t , J = 7.2 Hz, 4H, hexyl-CH 2 ), 2.68 (q, J = 7.2 Hz, 4H, CH 2 ), 2.66 (q, J = 7.2 Hz, 4H, CH 2 ), 1.67-1.60 (m, 4H, hexyl), 1.41-1.29 (m, 12H, hexyl), 1.25 (t, J = 7.2 Hz, 6H, CH 3 ), 1.23 (t, J = 7.2 Hz, 6H, CH 3 ), 0.91 (t, J = 7.2 Hz, 6H, hexyl-CH 3 );
13 C NMR (100 MHz, CDCl 3 , 20 ° C): δ 149.55, 131.55, 131.22, 130.96, 127.16, 126.06, 123.41, 61.56, 31.87, 31.53, 27.16, 22.82, 17.75, 17.62, 17.19, 16.31, 14.26;
IR (ATR): 2979, 2920, 2791, 2020, 1623, 1470, 1433, 1383, 1273, 1236, 1090, 888, 735, 703, 631, 572, 562 cm -1 ;
HRMS: m / z calculated for [M + H] + (C 36 H 54 N 4 ) 543.4426, found 543.4423.
以下の比較例１〜４の化合物（化合物（ＩＩａ）、化合物（ＩＩｂ）、化合物（ＩＩｃ）及び化合物（ＩＩｄ））は、実施例1及び２に記載の方法若しくはそれに準ずる方法、及び自体公知の方法（例えば、Setsune, J. et al., Tetrahedron Lett., 2006, 47, 7541-7544.参照）に従って、対応する原料化合物からそれぞれ製造した。 The following compounds of Comparative Examples 1 to 4 (Compound (IIa), Compound (IIb), Compound (IIc) and Compound (IId)) are described in Examples 1 and 2 or a method similar thereto, and are known per se. Each was prepared from the corresponding starting compound according to a method (see, eg, Setsune, J. et al., Tetrahedron Lett., 2006, 47, 7541-7544.).
比較例１
（（５，５’−（１，４−フェニレン）ビス（３，４−ジエチル−１Ｈ−ピロール−５，２−ジイル））ビス（メタニリリデン））ビス（フェニルアミン）（化合物（ＩＩａ））
Comparative Example 1
((5,5'-(1,4-phenylene) bis (3,4-diethyl-1H-pyrrole-5,2-diyl)) bis (methanilylidene)) bis (phenylamine) (compound (IIa))
1H NMR (400 MHz, CDCl3, 20℃): δ 8.35 (s, 2H, imine-H), 7.63 (s, 4H, phenylene-H), 7.43-7.39 (m, 4H, phenyl-H), 7.22-7.20 (m, 6H, phenyl-H), 2.75 (q, J = 7.6 Hz, 4H, CH2), 2.71 (q, J = 7.6 Hz, 4H, CH2), 1.29 (t, J = 7.6 Hz, 6H, CH3), 1.27 (t, J = 7.6 Hz, 6H CH3);
13C NMR (100 MHz, CDCl3, 20℃): δ 152.62, 147.68, 134.09, 131.68, 132.80, 129.35, 127.41, 127.06, 125.26, 124.38, 121.04, 17.77, 17.67, 17.39, 16.24;
HRMS: m/z calculated for [M+H]+ (C36H38N4) 527.3174, found for 527.3170;
IR (ATR): 2962, 2922, 2853, 2366, 2337, 1740, 1469, 1435, 1383, 1236, 1090, 889, 744, 698, 628, 596, 580, 569, 5559 cm-1.
1 1 H NMR (400 MHz, CDCl 3 , 20 ° C): δ 8.35 (s, 2H, imine-H), 7.63 (s, 4H, phenylene-H), 7.43-7.39 (m, 4H, phenyl-H), 7.22-7.20 (m, 6H, phenyl-H), 2.75 (q, J = 7.6 Hz, 4H, CH 2 ), 2.71 (q, J = 7.6 Hz, 4H, CH 2 ), 1.29 (t, J = 7.6) Hz, 6H, CH 3 ), 1.27 (t, J = 7.6 Hz, 6H CH 3 );
13 C NMR (100 MHz, CDCl 3 , 20 ° C): δ 152.62, 147.68, 134.09, 131.68, 132.80, 129.35, 127.41, 127.06, 125.26, 124.38, 121.04, 17.77, 17.67, 17.39, 16.24;
HRMS: m / z calculated for [M + H] + (C 36 H 38 N 4 ) 527.3174, found for 527.3170;
IR (ATR): 2962, 2922, 2853, 2366, 2337, 1740, 1469, 1435, 1383, 1236, 1090, 889, 744, 698, 628, 596, 580, 569, 5559 cm -1 .
比較例２
５，５’−（１，４−フェニレン）ビス（Ｎ−ベンジル−３，４−ジエチル−１Ｈ−ピロール−２−カルボキサミド）（化合物（ＩＩｂ））
Comparative Example 2
5,5'-(1,4-phenylene) bis (N-benzyl-3,4-diethyl-1H-pyrrole-2-carboxamide) (Compound (IIb))
1H NMR (400 MHz, DMSO-d6, 75℃): δ 10.76 (br, 2H, pyrrolic-NH), 7.96 (t, J = 5.6 Hz, 2H, amide-H), 7.57 (s, 4H, phenylene-H), 7.37-7.22 (m, 10H, phenyl-H), 4.47 (d, J = 5.6 Hz, 4H, benzyl-H), 2.79 (q, J = 7.6 Hz, 4H, CH2), 2.56 (q, J = 7.6 Hz, 4H, CH2), 1.17 (t, J = 7.6 Hz, 6H, CH3), 1.12 (t, J = 7.6 Hz, 6H, CH3);
13C NMR (100 MHz; DMSO; 348K): δ 160.47, 139.49, 130.89, 130.88, 128.96, 127.86, 127.12, 126.79, 126.35, 122.23, 121.02, 41.87, 17.14, 16.59, 15.65, 15.55;
HRMS: m/z calculated for [M+H]+ (C38H42N4O2) 587.3386, found for 587.3395;
IR (ATR): 3056, 2981, 2920, 1712, 1470, 1432, 1383, 1265, 1236, 1090, 892, 735, 704, 666, 630 cm-1.
1 H NMR (400 MHz, DMSO-d 6 , 75 ° C): δ 10.76 (br, 2H, pyrrolic-NH), 7.96 (t, J = 5.6 Hz, 2H, amide-H), 7.57 (s, 4H, phenylene-H), 7.37-7.22 (m, 10H, phenyl-H), 4.47 (d, J = 5.6 Hz, 4H, benzyl-H), 2.79 (q, J = 7.6 Hz, 4H, CH 2 ), 2.56 (q, J = 7.6 Hz, 4H, CH 2 ), 1.17 (t, J = 7.6 Hz, 6H, CH 3 ), 1.12 (t, J = 7.6 Hz, 6H, CH 3 );
13 C NMR (100 MHz; DMSO; 348K): δ 160.47, 139.49, 130.89, 130.88, 128.96, 127.86, 127.12, 126.79, 126.35, 122.23, 121.02, 41.87, 17.14, 16.59, 15.65, 15.55;
HRMS: m / z calculated for [M + H] + (C 38 H 42 N 4 O 2 ) 587.3386, found for 587.3395;
IR (ATR): 3056, 2981, 2920, 1712, 1470, 1432, 1383, 1265, 1236, 1090, 892, 735, 704, 666, 630 cm -1 .
比較例３
（Ｎ，Ｎ’Ｅ，Ｎ，Ｎ’Ｅ）−Ｎ，Ｎ’−（（５，５’−（１，３−フェニレン）ビス（３，４−ジエチル−１Ｈ−ピロール−５，２−ジイル））ビス（メタニリリデン））ビス（１−フェニルメタンアミン）（化合物（ＩＩｃ））
Comparative Example 3
(N, N'E, N, N'E) -N, N'-((5,5'-(1,3-phenylene) bis (3,4-diethyl-1H-pyrrole-5,2-diyl) )) Bis (methanilylidene)) Bis (1-phenylmethaneamine) (Compound (IIc))
1H NMR (400 MHz, CDCl3, 20℃): δ 8.21 (s, 2H, imine-H), 7.58 (s, 1H, phenylene-H), 7.46-7.21 (m, 13H, phenylene-H and phenyl-H), 4.64 (s, 4H, benzyl-H), 2.64 (q, J = 7.6 Hz, 4H, CH2), 2.62 (q, J = 7.6 Hz, 4H, CH2), 1.23 (t, J = 7.6 Hz, 6H, CH3), 1.17 (t, J = 7.6 Hz, 6H, CH3);
13C NMR (100M Hz, CDCl3): δ 150.65, 139.93, 133.50, 132.20, 131.82, 129.10, 128.73, 128.52, 127.92, 126.94, 125.88, 125.85, 123.42, 64.51, 17.64, 17.63, 17.25, 16.33;
HRMS: m/z calculated for [M+H]+(C38H42N4) 555.3487, found for 555.3492;
IR (ATR): 3055, 2977, 2920, 1636, 1468, 1435, 1383, 1265, 1236, 1090, 891, 734, 703, 630, 572, 563 cm-1.
1 H NMR (400 MHz, CDCl 3 , 20 ° C): δ 8.21 (s, 2H, imine-H), 7.58 (s, 1H, phenylene-H), 7.46-7.21 (m, 13H, phenylene-H and phenyl) -H), 4.64 (s, 4H, benzyl-H), 2.64 (q, J = 7.6 Hz, 4H, CH 2 ), 2.62 (q, J = 7.6 Hz, 4H, CH 2 ), 1.23 (t, J) = 7.6 Hz, 6H, CH 3 ), 1.17 (t, J = 7.6 Hz, 6H, CH 3 );
13 C NMR (100M Hz, CDCl 3 ): δ 150.65, 139.93, 133.50, 132.20, 131.82, 129.10, 128.73, 128.52, 127.92, 126.94, 125.88, 125.85, 123.42, 64.51, 17.64, 17.63, 17.25, 16.33;
HRMS: m / z calculated for [M + H] + (C 38 H 42 N 4 ) 555.3487, found for 555.3492;
IR (ATR): 3055, 2977, 2920, 1636, 1468, 1435, 1383, 1265, 1236, 1090, 891, 734, 703, 630, 572, 563 cm -1 .
比較例４
（Ｎ，Ｎ’Ｅ，Ｎ，Ｎ’Ｅ）−Ｎ，Ｎ’−（（５，５’−（チオフェン−２，５−ジイル）ビス（３，４−ジエチル−１Ｈ−ピロール−５，２−ジイル））ビス（メタニリリデン））ビス（１−フェニルメタンアミン）（化合物（ＩＩｄ））
Comparative Example 4
(N, N'E, N, N'E) -N, N'-((5,5'-(thiophene-2,5-diyl) bis (3,4-diethyl-1H-pyrrole-5,2) -Diyl)) bis (methanyllidene)) bis (1-phenylmethaneamine) (compound (IId))
1H NMR (400 MHz, CDCl3, 20℃): δ 8.22 (s, 2H, imine-H), 7.36-7.23 (m, 10H, phenyl-H), 7.07 (s, 2H, thiophene-H), 4.72 (s, 4H, benzyl-H), 2.67 (q, J = 7.6 Hz, 4H, CH2), 2.62 (q, J = 7.6 Hz, 4H, CH2), 1.23 (t, J = 7.6 Hz, 6H, CH3), 1.20 (t, J = 7.6 Hz, 6H, CH3);
13C NMR (100 MHz, CDCl3, 20℃): δ 150.41, 139.89, 133.35, 131.92, 128.65, 128.01, 127.12, 126.27, 125.88, 124.31, 123.86, 64.91, 17.93, 17.58, 17.13, 15.91;
HRMS: m/z calculated for [M+H]+(C36H40N4S) 561.3051, found for 561.3060;
IR (ATR): 3056, 2981, 2920, 1712, 1469, 1433, 1383, 1265, 1236, 1090, 892, 735, 704, 631, 590, 579, 566 cm-1.
1 1 H NMR (400 MHz, CDCl 3 , 20 ° C): δ 8.22 (s, 2H, imine-H), 7.36-7.23 (m, 10H, phenyl-H), 7.07 (s, 2H, thiophene-H), 4.72 (s, 4H, benzyl-H), 2.67 (q, J = 7.6 Hz, 4H, CH 2 ), 2.62 (q, J = 7.6 Hz, 4H, CH 2 ), 1.23 (t, J = 7.6 Hz, 6H, CH 3 ), 1.20 (t, J = 7.6 Hz, 6H, CH 3 );
13 C NMR (100 MHz, CDCl 3 , 20 ° C): δ 150.41, 139.89, 133.35, 131.92, 128.65, 128.01, 127.12, 126.27, 125.88, 124.31, 123.86, 64.91, 17.93, 17.58, 17.13, 15.91;
HRMS: m / z calculated for [M + H] + (C 36 H 40 N 4 S) 561.3051, found for 561.3060;
IR (ATR): 3056, 2981, 2920, 1712, 1469, 1433, 1383, 1265, 1236, 1090, 892, 735, 704, 631, 590, 579, 566 cm -1 .
実験例１
化合物（Ｉａ）、化合物（Ｉｂ）、化合物（ＩＩａ）、化合物（ＩＩｂ）、化合物（ＩＩｃ）及び化合物（ＩＩｄ）への酸の添加（酸の種類、及び添加する酸の当量比の変化に伴う）による各化合物の蛍光発光特性についての検討
Experimental Example 1
Addition of acid to compound (Ia), compound (Ib), compound (IIa), compound (IIb), compound (IIc) and compound (IId) (with changes in the type of acid and the equivalent ratio of the acid to be added) ) Examining the fluorescence emission characteristics of each compound
（試験方法１）
被験化合物を、１．８×１０−５Ｍ〜２．０×１０−５Ｍの濃度となるようにジクロロメタンに溶解させ、試験溶液を作製する。該試験溶液（３ｍＬ）を石英セルにとり、所定の当量（０当量、０．５当量、０．７当量、１．０当量、１．５当量、２．０当量、２．５当量及び３．０当量）の酸（トリフルオロ酢酸、塩酸又は硝酸）を添加し、混合後に、紫外-可視吸収スペクトル及び発光スペクトルを測定する。
(Test method 1)
The test compound, dissolved in dichloromethane at a concentration of 1.8 × 10 -5 M~2.0 × 10 -5 M, to prepare a test solution. The test solution (3 mL) was placed in a quartz cell and prescribed equivalents (0 equivalent, 0.5 equivalent, 0.7 equivalent, 1.0 equivalent, 1.5 equivalent, 2.0 equivalent, 2.5 equivalent and 3. Add 0 equivalents of an acid (trifluoroacetic acid, hydrochloric acid or nitrate), mix and then measure the ultraviolet-visible absorption spectrum and emission spectrum.
（試験方法２）
被験化合物を、２．８×１０−５Ｍの濃度となるようにジクロロメタンに溶解させ、試験溶液を作製する。該試験溶液（３ｍＬ）を石英セルにとり、所定の当量（０当量、２５０当量、５００当量、７５０当量、１０００当量、１２５０当量、１５００当量、１７５０当量及び２０００当量）の酸（塩化テトラ−ｎ−ブチルアンモニウム）を添加し、混合後に、紫外-可視吸収スペクトル及び発光スペクトルを測定する。
(Test method 2)
The test compound is dissolved in dichloromethane to a concentration of 2.8 × 10-5 M to prepare a test solution. The test solution (3 mL) was placed in a quartz cell and the acid (tetra-n-chloride) of a predetermined equivalent (0 equivalent, 250 equivalent, 500 equivalent, 750 equivalent, 1000 equivalent, 1250 equivalent, 1500 equivalent, 1750 equivalent and 2000 equivalent) was taken. Butylammonium) is added, and after mixing, the ultraviolet-visible absorption spectrum and the emission spectrum are measured.
（試験結果）
化合物（Ｉａ）、化合物（Ｉｂ）、化合物（ＩＩａ）、化合物（ＩＩｂ）、化合物（ＩＩｃ）及び化合物（ＩＩｄ）のそれぞれについて、試験方法１を実施した。それらの結果とそれらから算出した色度座標を図１〜３、５〜９に示す。また、化合物（Ｉａ）について、試験方法２を実施した。その結果とそれから算出した色度座標を図４に示す。
(Test results)
Test method 1 was carried out for each of compound (Ia), compound (Ib), compound (IIa), compound (IIb), compound (IIc) and compound (IId). The results and the chromaticity coordinates calculated from them are shown in FIGS. 1 to 3 and 5-9. In addition, test method 2 was carried out for compound (Ia). The result and the chromaticity coordinates calculated from it are shown in FIG.
図１〜５に示すように、本発明の化合物（Ｉ）（すなわち、化合物（Ｉａ）及び化合物（Ｉｂ））は、ジクロロメタン中で添加する酸の当量を変化させることにより発光色が変化することが確認された。特に、化合物（Ｉａ）又は化合物（Ｉｂ）と酸（トリフルオロ酢酸、塩酸又は硝酸）を当量比１：０．７〜１：１で混合した場合、或いは化合物（Ｉａ）と塩化テトラ−ｎ−ブチルアンモニウムを当量比１：５００で混合した場合に、該組成物は、国際照明委員会（ＣＩＥ：Commission Internationale de l'Eclairage)（１９３１）色度図における色度座標（ｘ，ｙ）、（０．３２〜０．３４，０．３２〜０．３４）を示し、紫外線（波長１０〜４００ｎｍ）を吸収して白色蛍光を発することが分かった。
これに対して、図６〜９に示すように、本発明の化合物（Ｉ）と化学構造が類似する化合物（ＩＩａ）、化合物（ＩＩｂ）、化合物（ＩＩｃ）及び化合物（ＩＩｄ）を用いた場合には、いずれの当量比で酸を添加しても白色蛍光を発しないことが分かった。
以上の結果から、白色蛍光を発現させるためには、化学構造の厳密な調整（すなわち、２個のイミン構造及び該イミンに隣接するメチレン基が必須であり、更に架橋芳香環は、１，４−フェニレンであることが必須である）が必要であることが分かった。
As shown in FIGS. 1 to 5, the compound (I) of the present invention (that is, the compound (Ia) and the compound (Ib)) changes its emission color by changing the equivalent of the acid added in dichloromethane. Was confirmed. In particular, when compound (Ia) or compound (Ib) and an acid (trifluoroacetic acid, hydrochloric acid or nitric acid) are mixed at an equivalent ratio of 1: 0.7 to 1: 1 or compound (Ia) and tetra-n-chloride When butylammonium was mixed at an equivalent ratio of 1: 500, the composition was found in the Commission Internationale de l'Eclairage (CIE) (1931) chromaticity coordinates (x, y), ( It was found that it showed 0.32 to 0.34, 0.32 to 0.34), absorbed ultraviolet rays (wavelength 10 to 400 nm), and emitted white fluorescence.
On the other hand, as shown in FIGS. 6 to 9, when compound (IIa), compound (IIb), compound (IIc) and compound (IId) having a chemical structure similar to that of compound (I) of the present invention are used. It was found that no white fluorescence was emitted when the acid was added at any equivalent ratio.
From the above results, in order to express white fluorescence, strict adjustment of the chemical structure (that is, two imine structures and a methylene group adjacent to the imine is essential, and the crosslinked aromatic rings are 1,4. -It was found that phenylene is essential).
本発明の化合物（Ｉ）は、各種酸を特定の当量比で添加するという簡便な操作により単一分子で白色蛍光を含め多彩な蛍光色を発現することができ、且つ耐久性にもコスト的にも優れた実用的な蛍光素子として有用である。白色蛍光材料は、蛍光インク、化粧品、塗料、洗剤等の界面活性剤、玩具、プラスチック材料の着色等の様々な用途が考えられる。それ故、発光量子収率が高く、質の高い白色蛍光を発することができる、本発明の化合物（Ｉ）又はその塩、或いはそれらを含有する蛍光組成物は、前記用途への応用が可能である。 The compound (I) of the present invention can express various fluorescent colors including white fluorescence with a single molecule by a simple operation of adding various acids at a specific equivalent ratio, and is also cost effective in terms of durability. It is also useful as an excellent and practical fluorescent element. The white fluorescent material can be used for various purposes such as coloring fluorescent inks, cosmetics, paints, surfactants such as detergents, toys, and plastic materials. Therefore, the compound (I) of the present invention or a salt thereof, which has a high emission quantum yield and can emit high-quality white fluorescence, or a fluorescence composition containing them can be applied to the above-mentioned applications. is there.
Claims (11)
Ｒ１及びＲ１’は、それぞれ独立して、水素原子、置換されていてもよいアルキル基、置換されていてもよいシクロアルキル基又は置換されていてもよいアリール基を示し、
Ｒ２、Ｒ２’ 、Ｒ３及びＲ３’は、それぞれ独立して、水素原子又は置換されていてもよいアルキル基を示し、
ｎ個のＲは、それぞれ独立して、アルキル基を示し、並びに
ｎは、０〜４の整数を示す。]
で表される化合物又はその塩、或いはそれらの溶媒和物。 Equation (I):
R 1 and R 1 'are each independently a hydrogen atom, a optionally substituted alkyl group, an optionally substituted cycloalkyl group or an optionally substituted aryl group,
R 2, R 2 ', R 3 and R 3' each independently represent a hydrogen atom or an optionally substituted alkyl group,
Each of the n Rs independently represents an alkyl group, and n represents an integer from 0 to 4. ]
A compound represented by, or a salt thereof, or a solvate thereof.
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