JPH09255686A - Styryl-8-hydroxy-quinolines and their production - Google Patents
Styryl-8-hydroxy-quinolines and their productionInfo
- Publication number
- JPH09255686A JPH09255686A JP8096248A JP9624896A JPH09255686A JP H09255686 A JPH09255686 A JP H09255686A JP 8096248 A JP8096248 A JP 8096248A JP 9624896 A JP9624896 A JP 9624896A JP H09255686 A JPH09255686 A JP H09255686A
- Authority
- JP
- Japan
- Prior art keywords
- group
- hydroxy
- styryl
- general formula
- following general
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- -1 (substituted) phenyl Chemical group 0.000 claims abstract description 21
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims abstract description 19
- 229960003540 oxyquinoline Drugs 0.000 claims abstract description 19
- 125000006239 protecting group Chemical group 0.000 claims abstract description 13
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 125000004663 dialkyl amino group Chemical group 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 125000006267 biphenyl group Chemical group 0.000 claims abstract description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 18
- 150000001875 compounds Chemical class 0.000 abstract description 6
- BKVXKVKAUFFGAM-UHFFFAOYSA-N 2-(2-phenylethenyl)quinolin-8-ol Chemical compound N1=C2C(O)=CC=CC2=CC=C1C=CC1=CC=CC=C1 BKVXKVKAUFFGAM-UHFFFAOYSA-N 0.000 abstract description 4
- 150000003934 aromatic aldehydes Chemical class 0.000 abstract 2
- 229940111121 antirheumatic drug quinolines Drugs 0.000 abstract 1
- 235000010290 biphenyl Nutrition 0.000 abstract 1
- 239000004305 biphenyl Substances 0.000 abstract 1
- 239000003446 ligand Substances 0.000 abstract 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000013078 crystal Substances 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000000859 sublimation Methods 0.000 description 4
- 230000008022 sublimation Effects 0.000 description 4
- 238000005092 sublimation method Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- RXIVMNWWOYEBMG-UHFFFAOYSA-N 2-[2-(4-phenylphenyl)ethenyl]quinolin-8-ol Chemical compound N1=C2C(O)=CC=CC2=CC=C1C=CC(C=C1)=CC=C1C1=CC=CC=C1 RXIVMNWWOYEBMG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- SLBPIHCMXPQAIQ-UHFFFAOYSA-N 8-hydroxyquinoline-2-carbaldehyde Chemical compound C1=C(C=O)N=C2C(O)=CC=CC2=C1 SLBPIHCMXPQAIQ-UHFFFAOYSA-N 0.000 description 2
- 150000004325 8-hydroxyquinolines Chemical class 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 1
- ISDBWOPVZKNQDW-UHFFFAOYSA-N 4-phenylbenzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC=CC=C1 ISDBWOPVZKNQDW-UHFFFAOYSA-N 0.000 description 1
- OQXVXPBDSJQYRR-UHFFFAOYSA-N 8-methoxy-2-methylquinoline Chemical compound C1=C(C)N=C2C(OC)=CC=CC2=C1 OQXVXPBDSJQYRR-UHFFFAOYSA-N 0.000 description 1
- ZLKGGEBOALGXJZ-UHFFFAOYSA-N 8-methoxyquinoline Chemical compound C1=CN=C2C(OC)=CC=CC2=C1 ZLKGGEBOALGXJZ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- PSLUFJFHTBIXMW-WYEYVKMPSA-N [(3r,4ar,5s,6s,6as,10s,10ar,10bs)-3-ethenyl-10,10b-dihydroxy-3,4a,7,7,10a-pentamethyl-1-oxo-6-(2-pyridin-2-ylethylcarbamoyloxy)-5,6,6a,8,9,10-hexahydro-2h-benzo[f]chromen-5-yl] acetate Chemical compound O([C@@H]1[C@@H]([C@]2(O[C@](C)(CC(=O)[C@]2(O)[C@@]2(C)[C@@H](O)CCC(C)(C)[C@@H]21)C=C)C)OC(=O)C)C(=O)NCCC1=CC=CC=N1 PSLUFJFHTBIXMW-WYEYVKMPSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 230000022244 formylation Effects 0.000 description 1
- 238000006170 formylation reaction Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LSACYLWPPQLVSM-UHFFFAOYSA-N isobutyric acid anhydride Chemical compound CC(C)C(=O)OC(=O)C(C)C LSACYLWPPQLVSM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、新規なスチリル−
８−ヒドロキシ−キノリン類とその製法に関する。TECHNICAL FIELD The present invention relates to a novel styryl group.
It relates to 8-hydroxy-quinolines and a method for producing the same.
【０００２】[0002]
【従来技術】従来、下記式2. Description of the Related Art Conventionally, the following formula
【化９】 で示される（８−キノリノラト）アルミニウム錯体（Ａ
ｌＱ）が有機ＥＬ素子の発光材料として広く使用されて
いるが、色素系の発光材料に比べて錯体系の発光材料は
少ない。Embedded image (8-quinolinolato) aluminum complex (A
Although 1Q) is widely used as a light emitting material for organic EL devices, there are few complex light emitting materials as compared with dye light emitting materials.
【０００３】[0003]
【発明が解決しようとする課題】そこで、本発明の目的
は、発光材料として有用な金属錯体を形成するのに適し
た新規なスチリル−８−ヒドロキシ−キノリン類、その
金属錯体およびその製法を提供する点にある。Therefore, an object of the present invention is to provide a novel styryl-8-hydroxy-quinoline compound suitable for forming a metal complex useful as a light emitting material, a metal complex thereof and a method for producing the same. There is a point to do.
【０００４】[0004]
【課題を解決するための手段】本発明の第一は、下記一
般式〔１〕The first aspect of the present invention is to provide the following general formula [1]:
【化１０】 （式中、Ｒ1、Ｒ2およびＲ3は、水素、アルキル基、ア
ルコキシ基、ジアルキルアミノ基、シアノ基、ハロゲン
および置換基を有することもある、フェニル基またはジ
フェニル基よりなる群から独立して選ばれた基である）
で示されるスチリル−８−ヒドロキシ−キノリン類に関
する。Embedded image (In the formula, R 1 , R 2 and R 3 are independently a group consisting of hydrogen, an alkyl group, an alkoxy group, a dialkylamino group, a cyano group, a halogen and a phenyl group which may have a substituent or a diphenyl group. Is the selected group)
With respect to styryl-8-hydroxy-quinolines.
【０００５】本発明の第二は、前記請求項１記載のスチ
リル−８−ヒドロキシ−キノリン類の金属錯体に関す
る。The second aspect of the present invention relates to a metal complex of styryl-8-hydroxy-quinoline according to claim 1.
【０００６】本発明の第三は、８−ヒドロキシ−キノリ
ン類の２位または４位にスチリル基を導入するのに適し
た極めて簡便な製法に関するものである。The third aspect of the present invention relates to an extremely simple production method suitable for introducing a styryl group at the 2-position or 4-position of 8-hydroxy-quinolines.
【０００７】すなわち、本発明の第三は、下記一般式
〔２〕That is, the third aspect of the present invention is the following general formula [2]
【化１１】 または下記一般式〔３〕Embedded image Or the following general formula [3]
【化１２】 （前記２つの式中、Ｒ1とＲ2は前記と同一であり、Ｒ4
は、メチル、エチルおよびプロピルよりなる群から選ば
れた基であり、Ａは水素または水酸基用保護基である）
で示される８−ヒドロキシ−２または４−アルキル−キ
ノリン類と、下記一般式〔４〕Embedded image (In the above two formulas, R 1 and R 2 are the same as above, and R 4
Is a group selected from the group consisting of methyl, ethyl and propyl, and A is a protective group for hydrogen or a hydroxyl group.)
8-hydroxy-2 or 4-alkyl-quinoline represented by the following general formula [4]
【化１３】 （式中、Ｒ3は前記と同一である）で示される芳香族ア
ルデヒドとを反応させ、Ａが保護基の場合はこれをとり
はずすことを特徴とする下記一般式〔５〕Embedded image (Wherein R 3 is the same as the above), and when A is a protecting group, it is removed, and the following general formula [5]
【化１４】 または、下記一般式〔６〕Embedded image Alternatively, the following general formula [6]
【化１５】 （式中、Ｒ1、Ｒ2およびＲ3は、前記と同一である）で
示されるスチリル−８−ヒドロキシ−キノリン類の製法
に関する。Embedded image (In the formula, R 1 , R 2 and R 3 are the same as the above) and relates to a process for producing a styryl-8-hydroxy-quinoline.
【０００８】本発明の第四は、下記一般式〔７〕A fourth aspect of the present invention is the following general formula [7]
【化１６】 （式中、Ｒ1、Ｒ2は、前記と同一である）で示されるホ
ルミル−８−ヒドロキシキノリン類と下記一般式〔８〕Embedded image (Wherein R 1 and R 2 are the same as above) and a formyl-8-hydroxyquinoline represented by the following general formula [8]
【化１７】 （式中、Ｒ3は、前記と同一であり、Ｘはハロゲン、Ｐ
ｈはフェニル基である)で示されるトリフェニルホスホ
ニオアルキル置換トリルハライドとを反応させ、Ａが保
護基の場合はこれをとりはずすことを特徴とする請求項
１記載のスチリル−８−ヒドロキシ−キノリン類の製法
に関する。Embedded image (In the formula, R 3 is the same as above, X is halogen, P
The styryl-8-hydroxy-quinoline according to claim 1, wherein when h is a protecting group, it is removed by reacting it with a triphenylphosphonioalkyl-substituted tolyl halide represented by the formula (h is a phenyl group). Regarding the manufacturing method of the kind.
【０００９】前記アルキル基、アルコキシ基、ジアルキ
ルアミノ基におけるアルキルとしては、メチル、エチ
ル、プロピル、ブチル、ｓｅｃ−ブチル、ｔ−ブチル、
ヘキシルなどを挙げることができ、フェニル基またはジ
フェニル基の置換基としては、アルキル基、アルコキシ
基、ジアルキルアミノ基、シアノ基またはハロゲンであ
ることができ、これらのアルキルは前記と同一のものを
挙げることができる。Examples of alkyl in the alkyl group, alkoxy group and dialkylamino group include methyl, ethyl, propyl, butyl, sec-butyl, t-butyl,
Hexyl and the like can be mentioned, and the substituent of the phenyl group or diphenyl group can be an alkyl group, an alkoxy group, a dialkylamino group, a cyano group or a halogen, and these alkyls are the same as those mentioned above. be able to.
【００１０】前記錯体を形成するための金属としては、
Ｌｉ，Ｎａ，Ｋ，Ｒｂ，Ｂｅ，Ｍｇ，Ｃａ，Ｓｒ，Ｂ
ａ，Ｚｎ，Ａｌ，Ｇａ，Ｉｎ，Ｓｃ，Ｙおよび希土類金
属を挙げることができる。As the metal for forming the complex,
Li, Na, K, Rb, Be, Mg, Ca, Sr, B
Mention may be made of a, Zn, Al, Ga, In, Sc, Y and rare earth metals.
【００１１】前記製法においては、無水酢酸、無水プロ
ピオン酸、無水イソ酪酸、無水イタコン酸、無水マレイ
ン酸、無水酪酸などの有機酸無水物の存在下に実施する
ことができる。また、もう１つの手段としては有機溶媒
中において有機塩基の存在下に実施することができる。
前記有機溶媒としては、ベンゼン、トルエン、キシレ
ン、クロロベンゼン、ジクロロベンゼン、トリクロロベ
ンゼン、メシチレン、ニトロベンゼンなどの芳香族系溶
媒であり、とりわけキシレンが好ましい。前記有機塩基
としては、モノ−，ジ−，トリ−アルキルアミン（アル
キルとしてはエチルかブチルが好ましい）、ピペリジン
のような脂環式アミン、ピリジンのような芳香族アミン
を挙げることができるが、とりわけエタノールアミン類
が好ましい。The above production process can be carried out in the presence of an organic acid anhydride such as acetic anhydride, propionic anhydride, isobutyric anhydride, itaconic anhydride, maleic anhydride, butyric anhydride. As another means, it can be carried out in an organic solvent in the presence of an organic base.
The organic solvent is an aromatic solvent such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, mesitylene and nitrobenzene, and xylene is particularly preferable. Examples of the organic base include mono-, di-, tri-alkylamines (ethyl or butyl is preferable as alkyl), alicyclic amines such as piperidine, and aromatic amines such as pyridine. Ethanolamines are particularly preferable.
【００１２】前記酸無水物を用いる反応においては、前
記酸無水物に加えて、酢酸のような有機酸のアルカリ金
属塩やアルカリ土類金属塩、例えば酢酸ナトリウム、酢
酸カリウムなどを存在させることが好ましい。とくにこ
れらの無水物が好ましい。これにより目的生成物の収率
を向上することができる。In the reaction using the acid anhydride, an alkali metal salt or an alkaline earth metal salt of an organic acid such as acetic acid, such as sodium acetate or potassium acetate, may be present in addition to the acid anhydride. preferable. In particular, these anhydrides are preferable. This can improve the yield of the desired product.
【００１３】前記保護基としては、メチル基、トリメチ
ルシリル基、ｔ−ブチルジメチルシリル基、ｔ−ブチル
ジフェニルシリル基、ｔ−ブチル基、トリチル基、テト
ラヒドロピラニル基、１−エトキシエチル基、メトキシ
メチル基などを挙げることができる。Examples of the protecting group include methyl group, trimethylsilyl group, t-butyldimethylsilyl group, t-butyldiphenylsilyl group, t-butyl group, trityl group, tetrahydropyranyl group, 1-ethoxyethyl group, methoxymethyl group. A group etc. can be mentioned.
【００１４】本発明の反応は、水が発生する反応であ
り、外部の湿気は好ましくないため、反応系の冷却系に
塩化カルシウムなどの乾燥剤を挿入したりして、水分を
除去することが好ましい。好ましくは、窒素雰囲気下、
とくに窒素気流下で行うことが望ましい。反応温度は、
有機酸無水物使用の場合は、通常８０〜１３９℃、好ま
しくは９５〜１０５℃、有機塩基を使用する場合は、通
常５０〜１５０℃、好ましくは１３０〜１４５℃、とく
に好ましくは１３８〜１４１℃である。Since the reaction of the present invention is a reaction in which water is generated and external humidity is not preferable, it is possible to remove moisture by inserting a desiccant such as calcium chloride into the cooling system of the reaction system. preferable. Preferably, under a nitrogen atmosphere,
It is particularly desirable to carry out under a nitrogen stream. The reaction temperature is
When an organic acid anhydride is used, it is usually 80 to 139 ° C, preferably 95 to 105 ° C, and when an organic base is used, it is usually 50 to 150 ° C, preferably 130 to 145 ° C, particularly preferably 138 to 141 ° C. Is.
【００１５】本発明において、一般式〔１〕で示される
スチリル−８−ヒドロキシキノリン誘導体を錯体化する
方法は、一般の錯体形成方法を転用することができる。
たとえば、相当する金属のハロゲン化物の水溶液あるい
は有機酸たとえば酢酸の金属塩と一般式〔１〕で示され
る化合物の有機溶媒溶液とを混合することにより錯体を
形成することができる。In the present invention, as a method for complexing the styryl-8-hydroxyquinoline derivative represented by the general formula [1], a general complex forming method can be diverted.
For example, the complex can be formed by mixing an aqueous solution of a corresponding metal halide or a metal salt of an organic acid such as acetic acid and a solution of a compound represented by the general formula [1] in an organic solvent.
【００１６】[0016]
【実施例】以下に実施例を挙げて本発明を説明するが、
本発明はこれにより限定されるものではない。The present invention will be described below with reference to examples.
The present invention is not limited to this.
【００１７】実施例１ メカニカルスターラー、水冷却管、水銀温度計のついた
１リットルの４つ口コルベンに、８−ヒドロキシキノリ
ン９５．５ｇ（０．６ｍｏｌ）、ベンズアルデヒド５
３．０ｇ（０．５ｍｏｌ）、無水酢酸３０６．５ｇ、無
水酢酸ナトリウム８．２ｇ（０．１ｍｏｌ）を入れ、オ
イルバス上において１００℃で２４時間反応させた。反
応式を示せば下記のとおりである。反応後、室温に冷却
し、析出した結晶を吸引、濾過により分離した。この結
晶をクロロホルム２００ｍｌに溶かし、これに水１００
ｍｌを加え、ついで１０％希アンモニア水で中和した。
中和後、さらに水１００ｍｌで２回洗浄し、分液後クロ
ロホルムを減圧下に回収し、黄色結晶７７ｇを回収し
た。さらにこの結晶にメタノール５００ｍｌで再結晶を
行ない、黄色結晶の２−スチリル−８−ヒドロキシキノ
リン７１．３ｇを得た。収率５７．１％、融点１０４．
８〜１０５．６℃。Example 1 95.5 g (0.6 mol) of 8-hydroxyquinoline and 5 benzaldehyde were placed in a 1-liter 4-port Kolben equipped with a mechanical stirrer, a water cooling tube, and a mercury thermometer.
3.0 g (0.5 mol), 306.5 g of acetic anhydride and 8.2 g (0.1 mol) of anhydrous sodium acetate were added, and the mixture was reacted at 100 ° C. for 24 hours on an oil bath. The reaction formula is shown below. After the reaction, the mixture was cooled to room temperature, and the precipitated crystals were separated by suction and filtration. Dissolve the crystals in 200 ml of chloroform and add 100 ml of water.
ml was added and then neutralized with 10% dilute aqueous ammonia.
After neutralization, the product was further washed twice with 100 ml of water, and after separation of the liquid, chloroform was recovered under reduced pressure to recover 77 g of yellow crystals. Further, the crystals were recrystallized with 500 ml of methanol to obtain 71.3 g of yellow crystals of 2-styryl-8-hydroxyquinoline. Yield 57.1%, melting point 104.
8-105.6 ° C.
【００１８】[0018]
【化１８】 Embedded image
【００１９】ビス（２−スチリル−８−キノリノラト）
亜鉛（II）錯体（ＺｎＳｑ2）の合成Bis (2-styryl-8-quinolinolato)
Synthesis of zinc (II) complex (ZnSq 2 )
【化１９】 塩化亜鉛（５ｍｍｏｌ、０．６８３ｇ）を水に、２−ス
チリル−８−ヒドロキシキノリン（１０ｍｍｏｌ、２．
７７ｇ）をテトラヒドロフラン（ＴＨＦ）にそれぞれ溶
解させ、水溶液中にＴＨＦ溶液をゆっくり滴下した。滴
下終了後１５分間撹拌を続けた。この時点でかなり析出
が起こっている。その後、水酸化ナトリウム水溶液で中
和した。その懸濁液をガラスフィルターを用いて濾過
し、粗結晶（２．２３ｇ、８０．０％）を得た。精製は
トレインサブリメーション法を用いた昇華精製によって
行った（６５．５％）。最終収率５２．４％。 ＺｎＳｑ2．の元素分析データ：Ｃ34Ｈ24Ｎ2Ｏ2Ｚｎ 計算値，Ｃ：７３．２０，Ｈ：４．３４，Ｎ：５．０
２； 実測値，Ｃ：７２．９９，Ｈ：４．２８，Ｎ：５．０５ この金属錯体はオレンジ色の発光材料として有用であっ
た。Embedded image Zinc chloride (5 mmol, 0.683 g) in water, 2-styryl-8-hydroxyquinoline (10 mmol, 2.
77 g) was dissolved in tetrahydrofuran (THF), and the THF solution was slowly dropped into the aqueous solution. After completion of dropping, stirring was continued for 15 minutes. At this point, considerable precipitation has occurred. Then, it neutralized with the sodium hydroxide aqueous solution. The suspension was filtered using a glass filter to obtain crude crystals (2.23 g, 80.0%). Purification was performed by sublimation purification using the train sublimation method (65.5%). Final yield 52.4%. ZnSq 2 . Elemental analysis data: C 34 H 24 N 2 O 2 Zn Calculated, C: 73.20, H: 4.34 , N: 5.0
2; measured value, C: 72.99, H: 4.28, N: 5.05 This metal complex was useful as an orange light emitting material.
【００２０】実施例２ メカニカルスターラー、水冷却管、水銀温度計のついた
３００ｍｌの４つ口コルベンに、８−メトキシキノリン
２４．８ｇ（１４４．１ｍｍｏｌ）、ｐ−フェニルベン
ズアルデヒド２５．０ｇ（１３７．２ｍｍｏｌ）、無水
酢酸７３．４ｇ、無水酢酸ナトリウム２．４ｇ（２９．
２ｍｍｏｌ）を入れ、オイルバス上において１００℃で
２４時間反応させた。反応式を示せば下記のとおりであ
る。反応後、室温に冷却し、析出した結晶を吸引、濾過
により分離した。この結晶を酢酸臭がなくなるまでエタ
ノールで洗浄し、淡黄褐色の目的物３６．９ｇを得た。
収率７８．３％、融点１８３．７〜１８５．０℃。Example 2 8-methoxyquinoline (24.8 g, 144.1 mmol) and p-phenylbenzaldehyde (25.0 g, 137. 2 mmol), acetic anhydride 73.4 g, anhydrous sodium acetate 2.4 g (29.
2 mmol) was added, and the mixture was reacted on an oil bath at 100 ° C. for 24 hours. The reaction formula is shown below. After the reaction, the mixture was cooled to room temperature, and the precipitated crystals were separated by suction and filtration. The crystals were washed with ethanol until the odor of acetic acid disappeared to obtain 36.9 g of a light yellowish brown target product.
Yield 78.3%, melting point 183.7-185.0 ° C.
【００２１】[0021]
【化２０】 Embedded image
【００２２】つぎに、前記保護基であるメチル基をとり
はずす。すなわち、メカニカルスターラー、水冷却管、
水銀温度計のついた５００ｍｌの４つ口フラスコに、４
７％臭化水素酸１７２．１ｇ（１．０ｍｏｌ）、氷酢酸
１８０ｍｌおよび先に得られたキノリン系化合物４５．
０ｇ（０．１５ｍｏｌ）を入れ、オイルバス上において
１００℃で２４時間反応させた。反応式を示せば下記の
とおりである。反応後、室温に冷却し、析出した結晶を
吸引、濾過により分離した。この結晶をクロロホルム１
０００ｍｌと水６００ｍｌに加え、ついで１０％希アン
モニア水で中和した。中和後、クロロホルム層を分液
し、水４００ｍｌで水洗し、水層を捨て、クロロホルム
層に無水硫酸ナトリウムを加えて脱水し、減圧下にクロ
ロホルムを回収し、４４．０ｇの残渣を得た。この残渣
にｎ−ブタノール６５０ｍｌおよび活性炭１５ｇを加
え、加熱溶解し、熱いうちに濾過し、ついで冷却により
結晶を生成させ、結晶を濾別し、ブタノール臭がなくな
るまでメタノールで洗浄し、２３．８ｇの淡黄色の２−
（４−フェニルスチリル）−８−ヒドロキシ−キノリン
を得た。Next, the methyl group, which is the protecting group, is removed. That is, mechanical stirrer, water cooling pipe,
4 in a 500 ml 4-neck flask with a mercury thermometer
172.1 g (1.0 mol) of 7% hydrobromic acid, 180 ml of glacial acetic acid and the quinoline compound 45.
0 g (0.15 mol) was added, and the mixture was reacted on an oil bath at 100 ° C for 24 hours. The reaction formula is shown below. After the reaction, the mixture was cooled to room temperature, and the precipitated crystals were separated by suction and filtration. Chloroform 1
In addition to 000 ml and 600 ml of water, the mixture was neutralized with 10% dilute aqueous ammonia. After neutralization, the chloroform layer was separated, washed with 400 ml of water, the aqueous layer was discarded, anhydrous sodium sulfate was added to the chloroform layer for dehydration, and chloroform was recovered under reduced pressure to obtain 44.0 g of a residue. . To this residue, 650 ml of n-butanol and 15 g of activated carbon were added, dissolved by heating, filtered while hot, and then crystals were formed by cooling, the crystals were separated by filtration, and washed with methanol until the smell of butanol disappeared, and 23.8 g The pale yellow 2-
(4-Phenylstyryl) -8-hydroxy-quinoline was obtained.
【００２３】[0023]
【化２１】 [Chemical 21]
【００２４】ビス〔２−（４−フェニルスチリル）−８
−キノリノラト〕亜鉛（II）錯体（ＺｎＰＳｑ2）の合
成Bis [2- (4-phenylstyryl) -8
-Quinolinolato] zinc (II) complex (ZnPSq 2 )
【化２２】 塩化亜鉛（３ｍｍｏｌ、０．４１ｇ）を水に、２−（４
−フェニルスチリル）−８−ヒドロキシキノリン（６ｍ
ｍｏｌ、１．９４ｇ）をＴＨＦにそれぞれ溶解させ、水
溶液中にＴＨＦ溶液をゆっくり滴下した。滴下終了後１
５分間撹拌を続けた。この時点でかなり析出が起こって
いる。その後、水酸化ナトリウム水溶液で中和した。そ
の懸濁液をガラスフィルターを用いて濾過し、粗結晶
（１．８３ｇ、８６．３％）を得た。精製はトレインサ
ブリメーション法を用いた昇華精製によって行った（１
４．７％）。最終収率１２．７％。 ＺｎＰＳｑ2．の元素分析データ：Ｃ46Ｈ32Ｎ2Ｏ2Ｚｎ 計算値，Ｃ：７７．８０，Ｈ：４．５４，Ｎ：３．９
５； 実測値，Ｃ：７７．６５，Ｈ：４．６２，Ｎ：３．９２ この金属錯体はオレンジ色の発光材料として有用であっ
た。Embedded image Zinc chloride (3 mmol, 0.41 g) in water, 2- (4
-Phenylstyryl) -8-hydroxyquinoline (6m
mol (1.94 g) was dissolved in THF, and the THF solution was slowly dropped into the aqueous solution. After dropping 1
Stirring was continued for 5 minutes. At this point, considerable precipitation has occurred. Then, it neutralized with the sodium hydroxide aqueous solution. The suspension was filtered using a glass filter to obtain crude crystals (1.83 g, 86.3%). Purification was performed by sublimation purification using the train sublimation method (1
4.7%). Final yield 12.7%. ZnPSq 2 . Elemental analysis data: C 46 H 32 N 2 O 2 Zn Calculated, C: 77.80, H: 4.54 , N: 3.9
5; measured value, C: 77.65, H: 4.62, N: 3.92 This metal complex was useful as an orange light emitting material.
【００２５】実施例３ ２−メチル−８−メトキシキノリン（０．２６ｍｏｌ、
４５．０ｇ）とｐ−（Ｎ，Ｎ−ジメチルアミノ）ベンズ
アルデヒド（０．２１ｍｏｌ、３２．０ｇ）とを工業用
キシレン２００ｍｌに溶かし、これにエタノールアミン
４．５ｍｌを加え、還流下２４時間反応させた。反応後
キシレンを回収し、得られた残渣１１４．２ｇに対し、
エタノール２４０ｍｌおよび水６０ｍｌを加え、再結晶
を行い、２９．６ｇの２−ｐ−（Ｎ，Ｎ−ジメチルアミ
ノスチリル）−８−メトキシキノリン結晶を得た（収率
４６．３％）。前記化合物の脱メチル化は、実施例２の
脱メチル化と同様にして４２時間行った。収率は４８％
であった。得られた２−ｐ−（Ｎ，Ｎ−ジメチルアミノ
スチリル）−８−ヒドロキシキノリンの融点は１６１〜
１６２℃（リグロインより）であった。前記化合物のＺ
ｎ錯体を実施例２と同様にして行ったところビス〔２−
ｐ−（Ｎ，Ｎ−ジメチルアミノスチリル）−８−キノリ
ノラト〕亜鉛（II）錯体が得られた。Example 3 2-Methyl-8-methoxyquinoline (0.26 mol,
45.0 g) and p- (N, N-dimethylamino) benzaldehyde (0.21 mol, 32.0 g) were dissolved in 200 ml of industrial xylene, to which 4.5 ml of ethanolamine was added and reacted under reflux for 24 hours. It was After the reaction, xylene was recovered, and to 114.2 g of the obtained residue,
240 ml of ethanol and 60 ml of water were added and recrystallization was performed to obtain 29.6 g of 2-p- (N, N-dimethylaminostyryl) -8-methoxyquinoline crystals (yield 46.3%). Demethylation of the above compound was carried out for 42 hours in the same manner as in Example 2. 48% yield
Met. The melting point of the obtained 2-p- (N, N-dimethylaminostyryl) -8-hydroxyquinoline is 161-
It was 162 ° C. (from ligroin). Z of the compound
When the n complex was carried out in the same manner as in Example 2, bis [2-
A p- (N, N-dimethylaminostyryl) -8-quinolinolato] zinc (II) complex was obtained.
【００２６】実施例４ ２−スチリル−８−キノリノラト−ナトリウム（Ｉ）錯
体（ＮａＳｑ2）の合成 水酸化ナトリウム（４ｍｍｏｌ、０．１６ｇ）を水に、
２−スチリル−８−ヒドロキシキノリン（４ｍｍｏｌ、
１．００ｇ）をＴＨＦに、それぞれ溶解させた。そし
て、水溶液中にＴＨＦ溶液をゆっくり滴下した。滴下終
了後１５分間撹拌した。この時点でかなり析出が起こっ
ている。この懸濁液をガラスフィルターを用いて濾過
し、粗結晶（０．８８ｇ、８１．３％）を得た。精製は
トレインサブリメーション法を用いた昇華精製によって
行った（１９．８％）。最終収率１６．７％。ＮａはＯ
Ｈ基の個所にＯＮａの形で導入されている。 ＮａＰＳｑ2．の元素分析データ：Ｃ17Ｈ12ＮＯＮａ 計算値，Ｃ：７５．８３，Ｈ：４．８６，Ｎ：５．２
０； 実測値，Ｃ：７５．６４，Ｈ：４．９１，Ｎ：５．１８Example 4 Synthesis of 2-styryl-8-quinolinolato-sodium (I) complex (NaSq 2 ) Sodium hydroxide (4 mmol, 0.16 g) was added to water.
2-styryl-8-hydroxyquinoline (4 mmol,
1.00 g) was dissolved in THF. Then, the THF solution was slowly dropped into the aqueous solution. After completion of dropping, the mixture was stirred for 15 minutes. At this point, considerable precipitation has occurred. This suspension was filtered using a glass filter to obtain crude crystals (0.88 g, 81.3%). Purification was performed by sublimation purification using the train sublimation method (19.8%). Final yield 16.7%. Na is O
It is introduced in the form of ONa at the position of H group. NaPSq 2 . Elemental analysis data: C 17 H 12 NONa Calculated, C: 75.83, H: 4.86 , N: 5.2
0; measured value, C: 75.64, H: 4.91, N: 5.18.
【００２７】実施例５ ２−（４−フェニル−スチリル）−８−キノリノラト−
ナトリウム（Ｉ）錯体（ＮａＰＳｑ2）の合成 水酸化ナトリウム（４ｍｍｏｌ、０．１６ｇ）を水に、
２−（４−フェニル−スチリル−８−ヒドロキシキノリ
ン（４ｍｍｏｌ、１．３２ｇ）をＴＨＦに、それぞれ溶
解させた。そして、水溶液中にＴＨＦ溶液をゆっくり滴
下した。滴下終了後１５分間撹拌した。この時点でかな
り析出が起こっている。この懸濁液をガラスフィルター
を用いて濾過し、粗結晶（１．２０ｇ、８５．４％）を
得た。精製はトレインサブリメーション法を用いた昇華
精製によって行った（１６．６％）。最終収率１４．３
％。 ＮａはＯＨ基の個所にＯＮａの形で導入されている。 ＮａＰＳｑ2．の元素分析データ：Ｃ23Ｈ16ＮＯＮａ 計算値，Ｃ：７８．６７，Ｈ：４．５９，Ｎ：３．９
９； 実測値，Ｃ：７８．６３，Ｈ：４．６２，Ｎ：４．０３Example 5 2- (4-phenyl-styryl) -8-quinolinolato-
Synthesis of Sodium (I) Complex (NaPSq 2 ) Sodium hydroxide (4 mmol, 0.16 g) was added to water.
2- (4-Phenyl-styryl-8-hydroxyquinoline (4 mmol, 1.32 g) was dissolved in THF, and the THF solution was slowly added dropwise to the aqueous solution, which was then stirred for 15 minutes. A considerable amount of precipitation occurred at this point.The suspension was filtered using a glass filter to obtain crude crystals (1.20 g, 85.4%) Purification was carried out by sublimation purification using a train sublimation method. Performed (16.6%) Final yield 14.3
%. Na is introduced in the form of ONa at the position of the OH group. NaPSq 2 . Elemental analysis data: C 23 H 16 NONa Calculated, C: 78.67, H: 4.59 , N: 3.9
9; measured value, C: 78.63, H: 4.62, N: 4.03.
【００２８】[0028]
【効果】本発明により、発光材料、電子輸送材料および
発光材料兼電子輸送材料としての有用性が大いに期待さ
れる新規なスチリル−８−ヒドロキシ−キノリンを提供
することができた。本発明により、新規化合物を製造す
るための新しい方法が提供できた。とくに請求項２の製
法は、ホルミル化物を経由することなく目的物を製造す
ることができるので、そのメリットは極めて大きい。According to the present invention, a novel styryl-8-hydroxy-quinoline, which is expected to be highly useful as a light emitting material, an electron transporting material, and a light emitting material and an electron transporting material, can be provided. The present invention has provided a new method for producing a novel compound. In particular, the manufacturing method of claim 2 can produce the target product without passing through the formylation product, and therefore has a great advantage.
【００２９】以下に、本発明の実施態様項を列挙する。 １．下記一般式〔１〕The embodiments of the present invention will be listed below. 1. The following general formula [1]
【化２３】 （式中、Ｒ1、Ｒ2およびＲ3は、水素、アルキル基、ア
ルコキシ基、ジアルキルアミノ基、シアノ基、ハロゲン
および置換基を有することもある、フェニル基またはジ
フェニル基よりなる群から独立して選ばれた基である）
で示されるスチリル−８−ヒドロキシ−キノリン類。 ２．前項１記載のスチリル−８−ヒドロキシ−キノリン
類の金属錯体。 ３．前記金属が遷移金属ではないものである前項２記載
のスチリル−８−ヒドロキシ−キノリン類の金属錯体。 ４．前記金属がＬｉ，Ｎａ，Ｋ，Ｒｂ，Ｂｅ，Ｍｇ，Ｃ
ａ，Ｓｒ，Ｂａ，Ｚｎ，Ａｌ，Ｇａ，Ｉｎ，Ｓｃ，Ｙお
よび希土類金属よりなる群から選ばれたものである前項
３記載のスチリル−８−ヒドロキシ−キノリン類の金属
錯体。 ５．下記一般式〔２〕Embedded image (In the formula, R 1 , R 2 and R 3 are independently a group consisting of hydrogen, an alkyl group, an alkoxy group, a dialkylamino group, a cyano group, a halogen and a phenyl group which may have a substituent or a diphenyl group. Is the selected group)
A styryl-8-hydroxy-quinoline represented by: 2. A metal complex of styryl-8-hydroxy-quinoline according to item 1 above. 3. The metal complex of styryl-8-hydroxy-quinoline according to the above item 2, wherein the metal is not a transition metal. 4. The metal is Li, Na, K, Rb, Be, Mg, C
The metal complex of styryl-8-hydroxy-quinoline according to the above item 3, which is selected from the group consisting of a, Sr, Ba, Zn, Al, Ga, In, Sc, Y and a rare earth metal. 5. The following general formula [2]
【化２４】 または下記一般式〔３〕Embedded image Or the following general formula [3]
【化２５】 （前記２つの式中、Ｒ1とＲ2は前記と同一であり、Ｒ4
は、メチル−エチルおよびプロピルよりなる群から選ば
れた基であり、Ａは水素または水酸基用保護基である）
で示される８−ヒドロキシ−２または４−アルキル−キ
ノリン類と、下記一般式〔４〕Embedded image (In the above two formulas, R 1 and R 2 are the same as above, and R 4
Is a group selected from the group consisting of methyl-ethyl and propyl, and A is a protective group for hydrogen or a hydroxyl group).
8-hydroxy-2 or 4-alkyl-quinoline represented by the following general formula [4]
【化２６】 （式中、Ｒ3は前記と同じである）で示される芳香族ア
ルデヒドとを反応させ、Ａが保護基の場合はこれをとり
はずすことを特徴とする下記一般式〔５〕Embedded image (Wherein R 3 is the same as above), and when A is a protecting group, it is removed and the following general formula [5]
【化２７】 または、下記一般式〔６〕Embedded image Alternatively, the following general formula [6]
【化２８】 （式中、Ｒ1、Ｒ2およびＲ3は、前記と同一である）で
示されるスチリル−８−ヒドロキシ−キノリン類の製
法。 ６．前記反応が、無水酢酸の存在下で行われるものであ
る前項５記載のスチリル−８−ヒドロキシ−キノリン類
の製法。 ７．前記反応が、無水酢酸および酢酸のアルカリ金属塩
またはアルカリ土類金属塩の存在下で行われるものであ
る前項５記載のスチリル−８−ヒドロキシ−キノリン類
の製法。 ８．下記一般式〔７〕Embedded image (In the formula, R 1 , R 2 and R 3 are the same as the above), and a method for producing a styryl-8-hydroxy-quinoline. 6. 6. The method for producing a styryl-8-hydroxy-quinoline according to the above item 5, wherein the reaction is carried out in the presence of acetic anhydride. 7. The method for producing a styryl-8-hydroxy-quinoline according to the above 5, wherein the reaction is carried out in the presence of acetic anhydride and an alkali metal salt or an alkaline earth metal salt of acetic acid. 8. The following general formula [7]
【化２９】 （式中、Ｒ1、Ｒ2は、前記と同一である）で示されるホ
ルミル−８−ヒドロキシキノリン類と下記一般式〔８〕Embedded image (Wherein R 1 and R 2 are the same as above) and a formyl-8-hydroxyquinoline represented by the following general formula [8]
【化３０】 （式中、Ｒ3は、前記と同一であり、Ｘはハロゲン、Ｐ
ｈはフェニル基である)で示されるトリフェニルホスホ
ニオアルキル置換トリルハライドとを反応させ、Ａが保
護基の場合はこれをとりはずすことを特徴とする前項１
記載のスチリル−８−ヒドロキシ−キノリン類の製法。 ９．前記反応が無水酢酸の存在下に行われるものである
前項８記載のスチリル−８−ヒドロキシ−キノリン類の
製法。 10．前記反応が無水酢酸および酢酸のアルカリ金属塩ま
たはアルカリ土類金属塩の存在下に行われるものである
前項８記載のスチリル−８−ヒドロキシ−キノリン類の
製法。Embedded image (In the formula, R 3 is the same as above, X is halogen, P
wherein h is a phenyl group), a triphenylphosphonioalkyl-substituted tolyl halide represented by the formula (1) is removed, and when A is a protecting group, it is removed.
Process for producing the described styryl-8-hydroxy-quinolines. 9. 9. The method for producing a styryl-8-hydroxy-quinoline according to the above item 8, wherein the reaction is carried out in the presence of acetic anhydride. Ten. 9. The method for producing styryl-8-hydroxy-quinolines according to the above item 8, wherein the reaction is carried out in the presence of acetic anhydride and an alkali metal salt or an alkaline earth metal salt of acetic acid.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｋ 11/06 Ｃ０９Ｋ 11/06 Ｚ Continuation of front page (51) Int.Cl. 6 Identification code Office reference number FI Technical display area C09K 11/06 C09K 11/06 Z
Claims (4)
ルコキシ基、ジアルキルアミノ基、シアノ基、ハロゲン
および置換基を有することもある、フェニル基またはジ
フェニル基よりなる群から独立して選ばれた基である）
で示されるスチリル−８−ヒドロキシ−キノリン類。[Claim 1] The following general formula [1] (In the formula, R 1 , R 2 and R 3 are independently a group consisting of hydrogen, an alkyl group, an alkoxy group, a dialkylamino group, a cyano group, a halogen and a phenyl group which may have a substituent or a diphenyl group. Is the selected group)
A styryl-8-hydroxy-quinoline represented by:
ロキシ−キノリン類の金属錯体。2. The metal complex of styryl-8-hydroxy-quinoline according to claim 1.
は、メチル、エチルおよびプロピルよりなる群から選ば
れた基であり、Ａは水素または水酸基用保護基である）
で示される８−ヒドロキシ−２または４−アルキル−キ
ノリン類と、下記一般式〔４〕 【化４】 （式中、Ｒ3は前記と同一である）で示される芳香族ア
ルデヒドとを反応させ、Ａが保護基の場合はこれをとり
はずすことを特徴とする下記一般式〔５〕 【化５】 または、下記一般式〔６〕 【化６】 （式中、Ｒ1、Ｒ2およびＲ3は、前記と同一である）で
示されるスチリル−８−ヒドロキシ−キノリン類の製
法。3. The following general formula [2]: Or the following general formula [3] (In the above two formulas, R 1 and R 2 are the same as above, and R 4
Is a group selected from the group consisting of methyl, ethyl and propyl, and A is a protective group for hydrogen or a hydroxyl group.)
8-hydroxy-2 or 4-alkyl-quinoline represented by the following general formula [4] (Wherein R 3 is the same as above) is reacted, and when A is a protecting group, this is removed, and the following general formula [5] Alternatively, the following general formula [6] (In the formula, R 1 , R 2 and R 3 are the same as the above), and a method for producing a styryl-8-hydroxy-quinoline.
ルミル−８−ヒドロキシ−キノリン類と下記一般式
〔８〕 【化８】 （式中、Ｒ3は、前記と同一であり、Ｘはハロゲン、Ｐ
ｈはフェニル基である)で示されるトリフェニルホスホ
ニオアルキル置換トリルハライドとを反応させ、Ａが保
護基の場合はこれをとりはずすことを特徴とする請求項
１記載のスチリル−８−ヒドロキシ−キノリン類の製
法。4. The following general formula [7]: (Wherein R 1 and R 2 are the same as above) and a formyl-8-hydroxy-quinoline compound represented by the following general formula [8] (In the formula, R 3 is the same as above, X is halogen, P
The styryl-8-hydroxy-quinoline according to claim 1, wherein when h is a protecting group, it is removed by reacting it with a triphenylphosphonioalkyl-substituted tolyl halide represented by the formula (h is a phenyl group). Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8096248A JPH09255686A (en) | 1996-03-26 | 1996-03-26 | Styryl-8-hydroxy-quinolines and their production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8096248A JPH09255686A (en) | 1996-03-26 | 1996-03-26 | Styryl-8-hydroxy-quinolines and their production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09255686A true JPH09255686A (en) | 1997-09-30 |
Family
ID=14159925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8096248A Pending JPH09255686A (en) | 1996-03-26 | 1996-03-26 | Styryl-8-hydroxy-quinolines and their production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09255686A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020092267A (en) * | 2002-09-30 | 2002-12-11 | 건설화학공업(주) | Light-emitting compound and display device adopting light-emitting compound as color-developing substance |
| WO2004073030A3 (en) * | 2003-02-06 | 2004-09-23 | Georgia Tech Res Inst | Metal 8-hydroxyquinoline -functionalized polymers and related materials and methods of making and using the same |
| US20100279340A1 (en) * | 2007-02-09 | 2010-11-04 | Nyu | Imaging agents for protein misfolding |
| JP2017506664A (en) * | 2014-02-28 | 2017-03-09 | オックスフォード・ユニヴァーシティ・イノヴェイション・リミテッド | Quinoline compounds |
-
1996
- 1996-03-26 JP JP8096248A patent/JPH09255686A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020092267A (en) * | 2002-09-30 | 2002-12-11 | 건설화학공업(주) | Light-emitting compound and display device adopting light-emitting compound as color-developing substance |
| WO2004073030A3 (en) * | 2003-02-06 | 2004-09-23 | Georgia Tech Res Inst | Metal 8-hydroxyquinoline -functionalized polymers and related materials and methods of making and using the same |
| US7105617B2 (en) | 2003-02-06 | 2006-09-12 | Georgia Tech Research Corporation | Metal 8-hydroxyquinoline-functionalized polymers and related materials and methods of making and using the same |
| US20100279340A1 (en) * | 2007-02-09 | 2010-11-04 | Nyu | Imaging agents for protein misfolding |
| US8158380B2 (en) * | 2007-02-09 | 2012-04-17 | New York University | Imaging agents for protein misfolding |
| JP2017506664A (en) * | 2014-02-28 | 2017-03-09 | オックスフォード・ユニヴァーシティ・イノヴェイション・リミテッド | Quinoline compounds |
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