JP5044180B2 - 5,6-benzocoumarin compounds - Google Patents
5,6-benzocoumarin compounds Download PDFInfo
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- JP5044180B2 JP5044180B2 JP2006261004A JP2006261004A JP5044180B2 JP 5044180 B2 JP5044180 B2 JP 5044180B2 JP 2006261004 A JP2006261004 A JP 2006261004A JP 2006261004 A JP2006261004 A JP 2006261004A JP 5044180 B2 JP5044180 B2 JP 5044180B2
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- FXRDPPFLWGSMQT-UHFFFAOYSA-N benzo[f]chromen-3-one Chemical class C1=CC=C2C(C=CC(O3)=O)=C3C=CC2=C1 FXRDPPFLWGSMQT-UHFFFAOYSA-N 0.000 title description 6
- -1 5,6-benzocoumarin compound Chemical class 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- NTCCNERMXRIPTR-UHFFFAOYSA-N 2-hydroxy-1-naphthaldehyde Chemical class C1=CC=CC2=C(C=O)C(O)=CC=C21 NTCCNERMXRIPTR-UHFFFAOYSA-N 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000007850 fluorescent dye Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000990 laser dye Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 150000004786 2-naphthols Chemical class 0.000 description 2
- KCUNIKPYRZUEHV-UHFFFAOYSA-N 5-formyl-6-hydroxynaphthalene-2-carboxylic acid Chemical compound O=CC1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KCUNIKPYRZUEHV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000001215 fluorescent labelling Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 1
- SXFWEYGOYHBDHW-UHFFFAOYSA-N C(C(C)(C)C)OC(=O)C=1C=C2C=CC(=C(C2=CC1)C=O)O Chemical compound C(C(C)(C)C)OC(=O)C=1C=C2C=CC(=C(C2=CC1)C=O)O SXFWEYGOYHBDHW-UHFFFAOYSA-N 0.000 description 1
- DBVNBEQUKGXBIA-UHFFFAOYSA-N C(C(C)C)OC(=O)C=1C=C2C=CC(=C(C2=CC1)C=O)O Chemical compound C(C(C)C)OC(=O)C=1C=C2C=CC(=C(C2=CC1)C=O)O DBVNBEQUKGXBIA-UHFFFAOYSA-N 0.000 description 1
- JXIGRCHFYFCGSC-UHFFFAOYSA-N C(C)(C)(C)OC(=O)C=1C=C2C=CC(=C(C2=CC1)C=O)O Chemical compound C(C)(C)(C)OC(=O)C=1C=C2C=CC(=C(C2=CC1)C=O)O JXIGRCHFYFCGSC-UHFFFAOYSA-N 0.000 description 1
- HQZRNNPROUFWBV-UHFFFAOYSA-N C(C)(C)(CC)OC(=O)C=1C=C2C=CC=C(C2=CC1)O Chemical compound C(C)(C)(CC)OC(=O)C=1C=C2C=CC=C(C2=CC1)O HQZRNNPROUFWBV-UHFFFAOYSA-N 0.000 description 1
- PPIOGPNQKDMBEC-UHFFFAOYSA-N C(C)(C)OC(=O)C=1C=C2C=CC(=C(C2=CC1)C=O)O Chemical compound C(C)(C)OC(=O)C=1C=C2C=CC(=C(C2=CC1)C=O)O PPIOGPNQKDMBEC-UHFFFAOYSA-N 0.000 description 1
- ZDPHLUJESWVDDH-UHFFFAOYSA-N C(C)(CC)OC(=O)C=1C=C2C=CC(=C(C2=CC1)C=O)O Chemical compound C(C)(CC)OC(=O)C=1C=C2C=CC(=C(C2=CC1)C=O)O ZDPHLUJESWVDDH-UHFFFAOYSA-N 0.000 description 1
- LYTQKBOWFHGBKF-UHFFFAOYSA-N C(C)OC(=O)C=1C=C2C=CC(=C(C2=CC1)C=O)O Chemical compound C(C)OC(=O)C=1C=C2C=CC(=C(C2=CC1)C=O)O LYTQKBOWFHGBKF-UHFFFAOYSA-N 0.000 description 1
- OQJJLXAWPZPEQN-UHFFFAOYSA-N C(CC(C)C)OC(=O)C=1C=C2C=CC(=C(C2=CC1)C=O)O Chemical compound C(CC(C)C)OC(=O)C=1C=C2C=CC(=C(C2=CC1)C=O)O OQJJLXAWPZPEQN-UHFFFAOYSA-N 0.000 description 1
- SFSYZVWMLLTXQJ-UHFFFAOYSA-N C(CC)OC(=O)C=1C=C2C=CC(=C(C2=CC1)C=O)O Chemical compound C(CC)OC(=O)C=1C=C2C=CC(=C(C2=CC1)C=O)O SFSYZVWMLLTXQJ-UHFFFAOYSA-N 0.000 description 1
- ZSPGZYYLHCQPMW-UHFFFAOYSA-N C(CCC(C)C)OC(=O)C=1C=C2C=CC(=C(C2=CC1)C=O)O Chemical compound C(CCC(C)C)OC(=O)C=1C=C2C=CC(=C(C2=CC1)C=O)O ZSPGZYYLHCQPMW-UHFFFAOYSA-N 0.000 description 1
- KBVYCMREONQKIQ-UHFFFAOYSA-N C(CCC)OC(=O)C=1C=C2C=CC(=C(C2=CC1)C=O)O Chemical compound C(CCC)OC(=O)C=1C=C2C=CC(=C(C2=CC1)C=O)O KBVYCMREONQKIQ-UHFFFAOYSA-N 0.000 description 1
- YXFAJDQZHIUSMB-UHFFFAOYSA-N C(CCCCC)OC(=O)C=1C=C2C=CC(=C(C2=CC1)C=O)O Chemical compound C(CCCCC)OC(=O)C=1C=C2C=CC(=C(C2=CC1)C=O)O YXFAJDQZHIUSMB-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- NFKGQHYUYGYHIS-UHFFFAOYSA-N dibutyl propanedioate Chemical compound CCCCOC(=O)CC(=O)OCCCC NFKGQHYUYGYHIS-UHFFFAOYSA-N 0.000 description 1
- MQXAJNXSULJYCY-UHFFFAOYSA-N dihexyl propanedioate Chemical compound CCCCCCOC(=O)CC(=O)OCCCCCC MQXAJNXSULJYCY-UHFFFAOYSA-N 0.000 description 1
- QRVSDVDFJFKYKA-UHFFFAOYSA-N dipropan-2-yl propanedioate Chemical compound CC(C)OC(=O)CC(=O)OC(C)C QRVSDVDFJFKYKA-UHFFFAOYSA-N 0.000 description 1
- LWIWFCDNJNZEKB-UHFFFAOYSA-N dipropyl propanedioate Chemical compound CCCOC(=O)CC(=O)OCCC LWIWFCDNJNZEKB-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 238000006170 formylation reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- UJDHUNQKAQSMKM-UHFFFAOYSA-N methyl 5-formyl-6-hydroxynaphthalene-2-carboxylate Chemical compound O=CC1=C(O)C=CC2=CC(C(=O)OC)=CC=C21 UJDHUNQKAQSMKM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Description
本発明は、新規な５，６−ベンゾクマリン化合物およびその製造方法に関する。 The present invention relates to a novel 5,6-benzocoumarin compound and a method for producing the same.
従来、多くの５，６−ベンゾクマリン化合物が知られており、これらの化合物は、染料、顔料等の着色用途（特許文献１および２を参照）、蛍光増白剤（特許文献３および４を参照）、抗菌剤（特許文献５を参照）など様々な分野で利用されている。 Conventionally, many 5,6-benzocoumarin compounds are known. These compounds are used for coloring dyes and pigments (see Patent Documents 1 and 2), fluorescent whitening agents (Patent Documents 3 and 4). And an antibacterial agent (see Patent Document 5).
これらの５，６−ベンゾクマリン化合物のなかでも、特に色材について、耐熱性、耐候性、色相などの種々の特性に関しての要求が多様化している。したがって、かかる化合物の選択の幅を広げるために、新たな５，６−ベンゾクマリン化合物の合成が望まれている。 Among these 5,6-benzocoumarin compounds, there are diversified demands regarding various properties such as heat resistance, weather resistance, hue, etc., particularly for color materials. Therefore, synthesis of new 5,6-benzocoumarin compounds is desired in order to expand the range of selection of such compounds.
また、種々の有機色素について蛍光性が確認されており、このような蛍光色素は電界発光素子、蛍光標識試薬、レーザー用色素、光学記録媒体、シンチレータなどの材料として様々な用途に使用されている。そこで、かかる用途に応じた種々の要求に応えるため、新たな蛍光色素の開発が望まれている。
本発明の目的は、電界発光素子、蛍光標識試薬、レーザー用色素、光学記録媒体、シンチレータなどの材料として有用な、新規な５，６−ベンゾクマリン化合物を提供することにある。 An object of the present invention is to provide a novel 5,6-benzocoumarin compound that is useful as a material for electroluminescent elements, fluorescent labeling reagents, laser dyes, optical recording media, scintillators, and the like.
本発明は、式［Ｉ］で表される新規な５，６−ベンゾクマリン化合物を提供する：
［式中、Ｘ１およびＸ２は、それぞれ、同一であっても異なっていてもよく、水素原子、または炭素原子数１〜６のアルキル基から選択される基；ただし、Ｘ２が炭素原子数１〜６のアルキル基である場合は、Ｘ１は水素原子ではない］。
The present invention provides a novel 5,6-benzocoumarin compound represented by the formula [I]:
[Wherein, X 1 and X 2 may be the same or different and are each selected from a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; provided that X 2 is a carbon atom; In the case of an alkyl group of 1 to 6, X 1 is not a hydrogen atom].
本発明の式［Ｉ］で表される５，６−ベンゾクマリン化合物において、Ｘ１およびＸ２は、それぞれ、同一であっても異なっていてもよく、水素原子、または炭素原子数１〜６のアルキル基から選択される基である。ただし、Ｘ２が炭素原子数１〜６のアルキル基である場合には、Ｘ１は水素原子ではない。 In the 5,6-benzocoumarin compound represented by the formula [I] of the present invention, X 1 and X 2 may be the same or different and each is a hydrogen atom or a carbon atom number of 1-6. A group selected from alkyl groups of: However, when X 2 is an alkyl group having 1 to 6 carbon atoms, X 1 is not a hydrogen atom.
Ｘ１および／またはＸ２が炭素原子数１〜６のアルキル基である場合の該アルキル基の具体例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ブチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、ｎ−ペンチル基、イソヘキシル基、またはｎ−ヘキシル基が挙げられる。 Specific examples of the alkyl group when X 1 and / or X 2 is an alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, isobutyl group, sec-butyl Group, tert-butyl group, n-butyl group, isopentyl group, neopentyl group, tert-pentyl group, n-pentyl group, isohexyl group, or n-hexyl group.
本発明の式［Ｉ］で表される５，６−ベンゾクマリン化合物の製造方法は特に制限されない。例えば、式［Ｉ］において、Ｘ１およびＸ２がともに炭素原子数１〜６のアルキル基である場合、または、Ｘ１が炭素原子数１〜６のアルキル基であり、Ｘ２が水素原子である場合、式［ＩＩ］で表される１−ホルミル−２−ナフトール誘導体と、式［ＩＩＩ］で表されるマロン酸ジエステルを、ピペリジンの存在下で反応させることによって、式［ＩＶ］で表されるベンゾクマリン化合物として製造することができる：
［式中、Ｘ２は水素原子、または炭素原子数１〜６のアルキル基から選択される基；Ｘ３は炭素原子数１〜６のアルキル基］。
The method for producing the 5,6-benzocoumarin compound represented by the formula [I] of the present invention is not particularly limited. For example, in the formula [I], when both X 1 and X 2 are alkyl groups having 1 to 6 carbon atoms, or X 1 is an alkyl group having 1 to 6 carbon atoms, and X 2 is a hydrogen atom In the formula [IV], a 1-formyl-2-naphthol derivative represented by the formula [II] and a malonic acid diester represented by the formula [III] are reacted in the presence of piperidine. It can be produced as the benzocoumarin compound represented:
[Wherein X 2 is a hydrogen atom or a group selected from alkyl groups having 1 to 6 carbon atoms; X 3 is an alkyl group having 1 to 6 carbon atoms].
式［ＩＩ］で表される、１−ホルミル−２−ナフトール誘導体は、２−ヒドロキシ−６−ナフトエ酸またはその炭素原子数１〜６であるアルキルエステルを、米国特許第４１１０３７５号明細書に記載の方法に従い、Ｄｕｆｆ法により１−ホルミル化することにより調製することが出来る。 The 1-formyl-2-naphthol derivative represented by the formula [II] is 2-hydroxy-6-naphthoic acid or an alkyl ester having 1 to 6 carbon atoms described in US Pat. No. 4,110,375. According to the method, it can be prepared by 1-formylation by the Duff method.
式［ＩＩ］で表される、１−ホルミル−２−ナフトール誘導体の具体例としては、１−ホルミル−２−ヒドロキシ−６−ナフトエ酸、１−ホルミル−２−ヒドロキシ−６−ナフトエ酸メチルエステル、１−ホルミル−２−ヒドロキシ−６−ナフトエ酸エチルエステル、１−ホルミル−２−ヒドロキシ−６−ナフトエ酸−ｎ−プロピルエステル、１−ホルミル−２−ヒドロキシ−６−ナフトエ酸イソプロピルエステル、１−ホルミル−２−ヒドロキシ−６−ナフトエ酸−ｎ−ブチルエステル、１−ホルミル−２−ヒドロキシ−６−ナフトエ酸イソブチルエステル、１−ホルミル−２−ヒドロキシ−６−ナフトエ酸−ｓｅｃ−ブチルエステル、１−ホルミル−２−ヒドロキシ−６−ナフトエ酸−ｔｅｒｔ−ブチルエステル、１−ホルミル−２−ヒドロキシ−６−ナフトエ酸−ｎ−ペンチルエステル、１−ホルミル−２−ヒドロキシ−６−ナフトエ酸イソペンチルエステル、１−ホルミル−２−ヒドロキシ−６−ナフトエ酸ネオペンチルエステル、１−ホルミル−２−ヒドロキシ−６−ナフトエ酸−ｔｅｒｔ−ペンチルエステル、１−ホルミル−２−ヒドロキシ−６−ナフトエ酸−ｎ−ヘキシルエステル、１−ホルミル−２−ヒドロキシ−６−ナフトエ酸イソヘキシルエステルなどが挙げられる。 Specific examples of the 1-formyl-2-naphthol derivative represented by the formula [II] include 1-formyl-2-hydroxy-6-naphthoic acid and 1-formyl-2-hydroxy-6-naphthoic acid methyl ester. 1-formyl-2-hydroxy-6-naphthoic acid ethyl ester, 1-formyl-2-hydroxy-6-naphthoic acid-n-propyl ester, 1-formyl-2-hydroxy-6-naphthoic acid isopropyl ester, 1 -Formyl-2-hydroxy-6-naphthoic acid-n-butyl ester, 1-formyl-2-hydroxy-6-naphthoic acid isobutyl ester, 1-formyl-2-hydroxy-6-naphthoic acid-sec-butyl ester, 1-formyl-2-hydroxy-6-naphthoic acid-tert-butyl ester, 1-formyl-2-hydroxy Roxy-6-naphthoic acid-n-pentyl ester, 1-formyl-2-hydroxy-6-naphthoic acid isopentyl ester, 1-formyl-2-hydroxy-6-naphthoic acid neopentyl ester, 1-formyl-2- Examples include hydroxy-6-naphthoic acid-tert-pentyl ester, 1-formyl-2-hydroxy-6-naphthoic acid-n-hexyl ester, 1-formyl-2-hydroxy-6-naphthoic acid isohexyl ester, and the like.
式［ＩＩＩ］で表されるマロン酸ジエステルは、マロン酸を常法に従いエステル化することにより調製できる。 The malonic acid diester represented by the formula [III] can be prepared by esterifying malonic acid according to a conventional method.
式［ＩＩＩ］で表されるマロン酸ジエステルの具体例としては、マロン酸ジメチル、マロン酸ジエチル、マロン酸ジ−ｎ−プロピル、マロン酸ジイソプロピル、マロン酸ジ−ｎ−ブチル、マロン酸ジ−ｎ−ペンチル、またはマロン酸ジ−ｎ−ヘキシルなどが挙げられる。これらの中では、反応性や入手の容易さなどから、マロン酸ジメチルまたはマロン酸ジエチルを用いるのが好ましい。 Specific examples of the malonic acid diester represented by the formula [III] include dimethyl malonate, diethyl malonate, di-n-propyl malonate, diisopropyl malonate, di-n-butyl malonate, di-n malonate. -Pentyl or di-n-hexyl malonate. Among these, it is preferable to use dimethyl malonate or diethyl malonate from the viewpoint of reactivity and availability.
式［ＩＩＩ］で表されるマロン酸ジエステルは、式［ＩＩ］で表される１−ホルミル−２−ナフトール誘導体１モルに対して、０．８〜５モル用いるのが好ましく、０．９〜３モル用いるのがより好ましく、１〜２モル用いるのが特に好ましい。 The malonic acid diester represented by the formula [III] is preferably used in an amount of 0.8 to 5 mol with respect to 1 mol of the 1-formyl-2-naphthol derivative represented by the formula [II], It is more preferable to use 3 mol, and it is particularly preferable to use 1 to 2 mol.
式［ＩＩ］で表される１−ホルミル−２−ナフトール誘導体と、式［ＩＩＩ］で表されるマロン酸ジエステルの反応に用いるピペリジンの量としては、式［ＩＩ］で表される１−ホルミル−２−ナフトール誘導体１モルに対して、０．３〜５モルが好ましく、０．４〜２モルがより好ましく、０．５〜１．５モルが特に好ましい。 The amount of piperidine used in the reaction between the 1-formyl-2-naphthol derivative represented by the formula [II] and the malonic acid diester represented by the formula [III] is 1-formyl represented by the formula [II]. The amount is preferably 0.3 to 5 mol, more preferably 0.4 to 2 mol, and particularly preferably 0.5 to 1.5 mol with respect to 1 mol of the 2-naphthol derivative.
式［ＩＩ］で表される１−ホルミル−２−ナフトール誘導体と、式［ＩＩＩ］で表されるマロン酸ジエステルの反応においては、所望により、酢酸を加えてもよく、酢酸を用いる場合の量は、ピペリジン１重量部に対して０．０１〜０．７重量部用いるのが好ましく、０．０５〜５重量部用いるのがより好ましい。 In the reaction of the 1-formyl-2-naphthol derivative represented by the formula [II] and the malonic acid diester represented by the formula [III], acetic acid may be added if desired, and the amount when acetic acid is used. Is preferably used in an amount of 0.01 to 0.7 parts by weight, more preferably 0.05 to 5 parts by weight, based on 1 part by weight of piperidine.
式［ＩＩ］で表される１−ホルミル−２−ナフトール誘導体と、式［ＩＩＩ］で表されるマロン酸ジエステルの反応に用いる溶媒は、反応が良好に進行する限り特に制限されない。好適な溶媒の例としては、メタノール、エタノール、ｎ−プロパノール、イソプロパノールなどのアルコール；テトラヒドロフラン、ジオキサン、ジイソプロピルエーテルなどのエーテル；ベンゼン、トルエン、キシレンなどの芳香族化合物；およびクロロホルム、テトラクロロエタンなどのハロゲン化アルカンが挙げられる。これらの中では、反応後の処理が容易であることなどから、メタノール、エタノール、ｎ−プロパノール、イソプロパノールなどのアルコールを用いるのがより好ましい。 The solvent used for the reaction of the 1-formyl-2-naphthol derivative represented by the formula [II] and the malonic acid diester represented by the formula [III] is not particularly limited as long as the reaction proceeds well. Examples of suitable solvents include: alcohols such as methanol, ethanol, n-propanol and isopropanol; ethers such as tetrahydrofuran, dioxane and diisopropyl ether; aromatic compounds such as benzene, toluene and xylene; and halogens such as chloroform and tetrachloroethane. And alkanes. Among these, it is more preferable to use alcohols such as methanol, ethanol, n-propanol, and isopropanol because treatment after the reaction is easy.
式［ＩＩ］で表される１−ホルミル−２−ナフトール誘導体と、式［ＩＩＩ］で表されるマロン酸ジエステルの反応に用いる溶媒の使用量は、式［ＩＩ］で表される１−ホルミル−２−ナフトール誘導体の重量に対して１〜５０倍重量用いるのが好ましく、２〜３０倍重量用いるのがより好ましく、３〜２０倍重量用いるのが特に好ましい。 The amount of the solvent used for the reaction of the 1-formyl-2-naphthol derivative represented by the formula [II] and the malonic acid diester represented by the formula [III] is 1-formyl represented by the formula [II]. It is preferable to use 1 to 50 times the weight of the 2-naphthol derivative, more preferably 2 to 30 times, and particularly preferably 3 to 20 times.
式［ＩＩ］で表される１−ホルミル−２−ナフトール誘導体と、式［ＩＩＩ］で表されるマロン酸ジエステルの反応は、通常、２０〜１５０℃、より好ましくは５０〜１００℃で行われ、反応時間としては１〜５０時間、より好ましくは２〜２０時間で行われる。 The reaction between the 1-formyl-2-naphthol derivative represented by the formula [II] and the malonic acid diester represented by the formula [III] is usually carried out at 20 to 150 ° C, more preferably 50 to 100 ° C. The reaction time is 1 to 50 hours, more preferably 2 to 20 hours.
反応時の圧力は特に限定されず、大気圧下、加圧下、または減圧下の何れの条件で行ってもよい。また、反応は窒素、アルゴンなどの不活性ガス雰囲気下で行うのが好ましい。 The pressure during the reaction is not particularly limited, and the reaction may be performed under any conditions of atmospheric pressure, increased pressure, or reduced pressure. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon.
反応終了後は、所望により、酢酸などを加え反応液を酸性化した後に、冷却、濃縮、水などの貧溶媒の添加などの方法によって、式［ＩＶ］で表される５，６−ベンゾクマリン化合物を反応液中に析出させ、これをろ過により回収し、所望により、再結晶、水や有機溶媒による洗浄などの方法によって精製すればよい。 After completion of the reaction, if desired, acetic acid or the like is added to acidify the reaction solution, followed by cooling, concentration, addition of a poor solvent such as water, and the like, by a method such as 5,6-benzocoumarin represented by the formula [IV]. The compound may be precipitated in the reaction solution, recovered by filtration, and purified by a method such as recrystallization or washing with water or an organic solvent, if desired.
一方、Ｘ１およびＸ２が共に水素原子である、式［Ｉ］で表される５，６−ベンゾクマリン化合物は、Ｘ２および／またはＸ３が炭素原子数１〜６のアルキル基である式［ＩＶ］で表される５，６−ベンゾクマリン化合物のカルボン酸エステル基を、例えば、水の存在下で、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウムなどの塩基により加水分解した後に、塩酸、硫酸などによって反応液を酸性化した後に析出物をろ過などの方法により回収することによって調製する事が出来る。 On the other hand, in the 5,6-benzocoumarin compound represented by the formula [I] in which X 1 and X 2 are both hydrogen atoms, X 2 and / or X 3 is an alkyl group having 1 to 6 carbon atoms. The carboxylic acid ester group of the 5,6-benzocoumarin compound represented by the formula [IV] was hydrolyzed with a base such as sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate in the presence of water, for example. Later, the reaction solution can be acidified with hydrochloric acid, sulfuric acid, etc., and then the precipitate can be collected by a method such as filtration.
このようにして得られる、式［Ｉ］で表される、５，６−ベンゾクマリン化合物は、溶液、固体、薄膜などの状態で、蛍光性を示すものであり、電界発光素子、蛍光標識試薬、レーザー用色素、光学記録媒体、シンチレータなどの材料として様々な用途において好適に使用される。 The 5,6-benzocoumarin compound represented by the formula [I] thus obtained exhibits fluorescence in the state of a solution, a solid, a thin film, and the like. It is preferably used in various applications as a material for laser dyes, optical recording media, scintillators and the like.
また、本発明の式［Ｉ］で表される、５，６−ベンゾクマリン化合物は、反応性に富み、種々の基に変換可能であるカルボキシル基またはエステル化されたカルボキシル基を２つ有する事から、さらに多種の５，６−ベンゾクマリン誘導体を合成するための原料としても有用である。 Further, the 5,6-benzocoumarin compound represented by the formula [I] of the present invention is rich in reactivity and has two carboxyl groups or esterified carboxyl groups that can be converted into various groups. From this, it is also useful as a raw material for synthesizing more various 5,6-benzocoumarin derivatives.
以下、実施例により本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail by way of examples.
１−ホルミル−２−ヒドロキシ−６−ナフトエ酸１５ｇ（６９．４ｍｍｏｌ）、マロン酸ジエチル１２．２ｇ（７６．２ｍｍｏｌ）、ピペリジン２５．９ｇ（６９．５ｍｍｏｌ）、酢酸０．６ｇ（１０．０ｍｍｏｌ）およびエタノール７５ｇを容量２００ｍｌの、温度計およびジムロート冷却器を備えた反応容器に仕込み、窒素雰囲気下に反応液を攪拌しながら、７０〜８０℃に加熱し、６時間反応を行った。 1-formyl-2-hydroxy-6-naphthoic acid 15 g (69.4 mmol), diethyl malonate 12.2 g (76.2 mmol), piperidine 25.9 g (69.5 mmol), acetic acid 0.6 g (10.0 mmol) Then, 75 g of ethanol was charged into a reaction vessel having a capacity of 200 ml and equipped with a thermometer and a Dimroth condenser, and the reaction solution was heated to 70 to 80 ° C. while stirring the reaction solution in a nitrogen atmosphere, and reacted for 6 hours.
反応終了後、酢酸４．１ｇを加え、６０℃にて３０分攪拌保持した。次いで、反応液を１０℃まで冷却し、析出物をろ過により回収し、得られた結晶をメタノール中に懸濁し洗浄した。洗浄後の結晶をろ過により回収しこれを乾燥し、式［１］の５，６−ベンゾクマリン化合物の粗結晶１８．４ｇを得た。 After completion of the reaction, 4.1 g of acetic acid was added, and the mixture was stirred and held at 60 ° C. for 30 minutes. Next, the reaction solution was cooled to 10 ° C., the precipitate was collected by filtration, and the obtained crystal was suspended in methanol and washed. The washed crystal was collected by filtration and dried to obtain 18.4 g of a crude crystal of the 5,6-benzocoumarin compound of the formula [1].
得られた粗結晶１８．４ｇをＮ，Ｎ−ジメチルホルムアミド９２ｇに加え、６０℃にて攪拌した後、室温まで冷却し、式［１］の５，６−ベンゾクマリン化合物をろ過により回収した。次いで、得られた結晶をメタノールにより洗浄した後に乾燥し、式［１］の５，６−ベンゾクマリン化合物の淡黄色の結晶１５．８ｇ（収率７２．６％）を得た。 18.4 g of the obtained crude crystals were added to 92 g of N, N-dimethylformamide, stirred at 60 ° C., cooled to room temperature, and the 5,6-benzocoumarin compound of the formula [1] was recovered by filtration. Next, the obtained crystals were washed with methanol and dried to obtain 15.8 g (yield 72.6%) of pale yellow crystals of the 5,6-benzocoumarin compound of the formula [1].
式［１］のベンゾクマリン化合物の赤外吸収スペクトルを図１に示す。 An infrared absorption spectrum of the benzocoumarin compound of the formula [1] is shown in FIG.
本実施例により得られた式［１］の５，６−ベンゾクマリン化合物は、固体、溶液、薄膜（蒸着膜）の何れにおいても蛍光性を示すものであった。固体、溶液（１．９μＭ、Ｎ，Ｎ−ジメチルホルムアミド）、薄膜（蒸着膜、膜厚１００ｎｍ）の分光蛍光光度計（株式会社日立ハイテクノロジーズ、Ｆ−４５００）を用いて測定した蛍光スペクトルの波形を図２に示す。 The 5,6-benzocoumarin compound of the formula [1] obtained in this example exhibited fluorescence in any of solid, solution, and thin film (deposited film). Waveform of fluorescence spectrum measured using a spectrofluorophotometer (Hitachi High-Technologies Corporation, F-4500) of solid, solution (1.9 μM, N, N-dimethylformamide), thin film (deposition film, film thickness 100 nm) Is shown in FIG.
なお、蒸着膜の作成は、アセトンにより超音波洗浄したスライドガラス上に、アルバック社製小型真空蒸着装置ＰＶＣ−２６０を用い、真空度８．６ｘ１０−４Ｐａ〜６．８ｘ１０−４Ｐａにて、成膜速度、０．３８ｎｍ／ｓにて行った。所望の膜厚への調整は、アルバック社製水晶振動式膜厚計ＣＲＴＭ−６０００にて成膜速度をモニターしシャッターの開閉により行った。 Note that creation of the deposited film is on the slide glass was ultrasonically cleaned with acetone, using a ULVAC Inc. small vacuum evaporation apparatus PVC-260, at a vacuum degree of 8.6x10 -4 Pa~6.8x10 -4 Pa, The deposition rate was 0.38 nm / s. Adjustment to the desired film thickness was performed by opening and closing the shutter while monitoring the film formation speed with a quartz vibration type film thickness meter CRTM-6000 manufactured by ULVAC.
Claims (3)
［式中、Ｘ１およびＸ２は、それぞれ、同一であっても異なっていてもよく、水素原子、または炭素原子数１〜６のアルキル基から選択される基；ただし、Ｘ２が炭素原子数１〜６のアルキル基である場合は、Ｘ１は水素原子ではない］。 5,6-benzocoumarin compound represented by the formula [I]:
[Wherein, X 1 and X 2 may be the same or different and are each selected from a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; provided that X 2 is a carbon atom; In the case of an alkyl group of 1 to 6, X 1 is not a hydrogen atom].
［式中、Ｘ２は水素原子、または炭素原子数１〜６のアルキル基から選択される基；Ｘ３は炭素原子数１〜６のアルキル基］。 Represented by the formula [IV], comprising reacting the 1-formyl-2-naphthol derivative represented by the formula [II] with the malonic acid diester represented by the formula [III] in the presence of piperidine. Method for producing benzocoumarin compound:
[Wherein X 2 is a hydrogen atom or a group selected from alkyl groups having 1 to 6 carbon atoms; X 3 is an alkyl group having 1 to 6 carbon atoms].
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