JP2009209120A - Aromatic compound and ultraviolet absorber - Google Patents
Aromatic compound and ultraviolet absorber Download PDFInfo
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- JP2009209120A JP2009209120A JP2008056347A JP2008056347A JP2009209120A JP 2009209120 A JP2009209120 A JP 2009209120A JP 2008056347 A JP2008056347 A JP 2008056347A JP 2008056347 A JP2008056347 A JP 2008056347A JP 2009209120 A JP2009209120 A JP 2009209120A
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- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 77
- 239000006097 ultraviolet radiation absorber Substances 0.000 title claims abstract description 12
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000003277 amino group Chemical group 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 abstract description 32
- 239000002994 raw material Substances 0.000 abstract description 11
- 239000001257 hydrogen Substances 0.000 abstract 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 21
- 239000000047 product Substances 0.000 description 21
- 238000001228 spectrum Methods 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- AUJXJFHANFIVKH-GQCTYLIASA-N trans-methylferulate Chemical compound COC(=O)\C=C\C1=CC=C(O)C(OC)=C1 AUJXJFHANFIVKH-GQCTYLIASA-N 0.000 description 18
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- KSEBMYQBYZTDHS-HWKANZROSA-N ferulic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000013067 intermediate product Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- JTLOUXXZZFFBBW-UHFFFAOYSA-N isoferulic acid methyl ester Natural products COC(=O)C=CC1=CC=C(OC)C(O)=C1 JTLOUXXZZFFBBW-UHFFFAOYSA-N 0.000 description 9
- AUJXJFHANFIVKH-UHFFFAOYSA-N methyl cis-ferulate Natural products COC(=O)C=CC1=CC=C(O)C(OC)=C1 AUJXJFHANFIVKH-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- KSEBMYQBYZTDHS-HWKANZROSA-M (E)-Ferulic acid Natural products COC1=CC(\C=C\C([O-])=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-M 0.000 description 8
- 229940114124 ferulic acid Drugs 0.000 description 8
- 235000001785 ferulic acid Nutrition 0.000 description 8
- KSEBMYQBYZTDHS-UHFFFAOYSA-N ferulic acid Natural products COC1=CC(C=CC(O)=O)=CC=C1O KSEBMYQBYZTDHS-UHFFFAOYSA-N 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- QURCVMIEKCOAJU-UHFFFAOYSA-N trans-isoferulic acid Natural products COC1=CC=C(C=CC(O)=O)C=C1O QURCVMIEKCOAJU-UHFFFAOYSA-N 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- -1 2-ethyl-1-hexyl Chemical group 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012785 packaging film Substances 0.000 description 3
- 229920006280 packaging film Polymers 0.000 description 3
- NGSWKAQJJWESNS-UHFFFAOYSA-N 4-coumaric acid Chemical compound OC(=O)C=CC1=CC=C(O)C=C1 NGSWKAQJJWESNS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 150000003872 salicylic acid derivatives Chemical class 0.000 description 2
- 210000003491 skin Anatomy 0.000 description 2
- QAIPRVGONGVQAS-DUXPYHPUSA-N trans-caffeic acid Chemical compound OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- ACEAELOMUCBPJP-UHFFFAOYSA-N (E)-3,4,5-trihydroxycinnamic acid Natural products OC(=O)C=CC1=CC(O)=C(O)C(O)=C1 ACEAELOMUCBPJP-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- WJHQNSWJECNPND-ZZXKWVIFSA-N COc1c2[o]c(-c(cc3)cc(OC)c3O)c(C(O)=O)c2cc(/C=C/C(O)=O)c1 Chemical compound COc1c2[o]c(-c(cc3)cc(OC)c3O)c(C(O)=O)c2cc(/C=C/C(O)=O)c1 WJHQNSWJECNPND-ZZXKWVIFSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 125000005075 adamantyloxy group Chemical group C12(CC3CC(CC(C1)C3)C2)O* 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000004883 caffeic acid Nutrition 0.000 description 1
- 229940074360 caffeic acid Drugs 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid group Chemical class C(C=CC1=CC=CC=C1)(=O)O WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- QAIPRVGONGVQAS-UHFFFAOYSA-N cis-caffeic acid Natural products OC(=O)C=CC1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 210000004207 dermis Anatomy 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ATJVZXXHKSYELS-FNORWQNLSA-N ethyl (e)-3-(4-hydroxy-3-methoxyphenyl)prop-2-enoate Chemical compound CCOC(=O)\C=C\C1=CC=C(O)C(OC)=C1 ATJVZXXHKSYELS-FNORWQNLSA-N 0.000 description 1
- 229940027504 ethyl ferulate Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- ATJVZXXHKSYELS-UHFFFAOYSA-N ferulic acid ethyl ester Natural products CCOC(=O)C=CC1=CC=C(O)C(OC)=C1 ATJVZXXHKSYELS-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 238000012746 preparative thin layer chromatography Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229940058287 salicylic acid derivative anticestodals Drugs 0.000 description 1
- PCMORTLOPMLEFB-ONEGZZNKSA-N sinapic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-ONEGZZNKSA-N 0.000 description 1
- PCMORTLOPMLEFB-UHFFFAOYSA-N sinapinic acid Natural products COC1=CC(C=CC(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-UHFFFAOYSA-N 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 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
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Abstract
Description
本発明は、芳香族化合物及び紫外線吸収剤に関するものである。 The present invention relates to an aromatic compound and an ultraviolet absorber.
地上に降り注ぐ紫外線はその波長の違いにより中波長のＵＶ−Ｂ（２９０ｎｍ〜３２０ｎｍ）ならびに長波長のＵＶ−Ａ（３２０ｎｍ〜４００ｎｍ）に分けられるが、それぞれ生体やプラスチックなどに様々な影響を及ぼすことが知られている。例えば生体に対しては、ＵＶ−Ｂは皮膚内へ透過することにより水泡の形成や色素の沈着を誘発するとされており、ＵＶ−Ａは人間の真皮にまで到達することで即時黒化作用を引き起こし、さらには皮膚の老化やガン化を促進させるということが知られている。 Ultraviolet rays falling on the ground can be divided into medium-wavelength UV-B (290 nm to 320 nm) and long-wavelength UV-A (320 nm to 400 nm) depending on the difference in wavelength. It has been known. For example, for the living body, UV-B is said to induce formation of water bubbles and pigmentation by permeating into the skin, and UV-A has an immediate blackening action by reaching the human dermis. It is known to cause aging and canceration of the skin.
また、各種プラスチックに対しては、屋外においては太陽光、そして屋内においては蛍光灯からの紫外線に暴露されることにより、プラスチック中の官能基や残留触媒が励起され、これらはプラスチックの劣化を促進し、その結果、プラスチック自身の寿命を短くする。更に、紫外線は、透明な包装用フィルムにより包装された食品や衣類の該包装フィルムを透過して鮮度の低下や変質を引き起こしている。 For various plastics, exposure to sunlight outdoors and ultraviolet rays from fluorescent lights indoors excites functional groups and residual catalysts in the plastic, which promotes plastic deterioration. As a result, the life of the plastic itself is shortened. Furthermore, the ultraviolet rays permeate through the packaging film of food and clothing packaged with a transparent packaging film, causing a decrease in freshness and alteration.
このように有害な紫外線から生体やプラスチックなどを保護するため、従来サリチル酸誘導体、ベンゾフェノン誘導体、ベンゾトリアゾール誘導体、安息香酸誘導体など、主に枯渇資源である原油等を原料とする紫外線吸収剤が利用されてきた。また、天然由来の紫外線吸収剤としては、米ぬか由来物質であるフェルラ酸およびその誘導体が存在している。この米ぬか由来物質であるフェルラ酸等の紫外線吸収剤を化粧品組成物に利用した技術が下記特許文献１に記載されている。 In order to protect living organisms and plastics from such harmful ultraviolet rays, ultraviolet absorbers mainly made from crude oil, which is a depleted resource, such as salicylic acid derivatives, benzophenone derivatives, benzotriazole derivatives, and benzoic acid derivatives have been used. I came. In addition, as a naturally occurring ultraviolet absorber, ferulic acid and its derivatives, which are rice bran-derived substances, exist. Patent Document 1 listed below discloses a technique in which an ultraviolet absorber such as ferulic acid, which is a substance derived from rice bran, is used in a cosmetic composition.
しかしながら、上記サリチル酸誘導体等の原油等を原料とする従来の紫外線吸収剤は、４００ｎｍ付近の長波長の紫外線を効率的に吸収することができず、また、枯渇資源である原油などを原料とするために今後の原油価格の上昇も懸念されるだけでなく、クリーンな社会の構築を進めるうえで解決していかなくてはならない問題である。 However, conventional ultraviolet absorbers using crude oil such as the salicylic acid derivative as a raw material cannot efficiently absorb ultraviolet rays having a long wavelength around 400 nm, and crude oil as a depleted resource is used as a raw material. Therefore, it is not only a concern about the future rise in crude oil prices, but also a problem that must be solved in order to build a clean society.
また、フェルラ酸およびその誘導体を用いた天然由来の紫外線吸収剤は、中波長のＵＶ−Ｂに吸収特性が対応しており、長波長のＵＶ−Ａ側に吸収端を有する紫外線吸収剤としては不十分である。 Naturally derived ultraviolet absorbers using ferulic acid and derivatives thereof have absorption characteristics corresponding to medium wavelength UV-B, and as ultraviolet absorbers having an absorption edge on the long wavelength UV-A side. It is insufficient.
本発明は、上記した従来の問題点に鑑みてなされたものであって、広い波長範囲で紫外線を吸収し、かつ天然由来原料を用いた化合物及びこの化合物を用いた紫外線吸収剤の提供を目的とする。 The present invention has been made in view of the above-described conventional problems, and an object of the present invention is to provide a compound that absorbs ultraviolet rays in a wide wavelength range and uses a naturally-derived raw material, and an ultraviolet absorber using the compound. And
上記目的を達成するために、本発明に係る芳香族化合物は、式（１）で表される芳香族化合物である。
また、本発明に係る芳香族化合物は、式（２）で表される芳香族化合物である。
そして、本発明に係る芳香族化合物は、式（３）で表される芳香族化合物である。
更に、本発明に係る紫外線吸収剤は、前記した各構成の芳香族化合物を含有することを特徴とするものである。 Furthermore, the ultraviolet absorber according to the present invention is characterized by containing the aromatic compound having the above-described constitution.
本発明に係る紫外線吸収剤によれば、式（１）、（２）、（３）のいずれかで示す芳香族化合物を含有するので、広い波長範囲で紫外線を吸収可能であり、かつ非石油由来物質として安定供給可能な桂皮酸誘導体から合成されることから天然由来原料から生成される物質を用いた紫外線吸収剤を提供することができる。 The ultraviolet absorber according to the present invention contains an aromatic compound represented by any one of formulas (1), (2), and (3), and therefore can absorb ultraviolet rays in a wide wavelength range and is non-petroleum. Since it is synthesized from a cinnamic acid derivative that can be stably supplied as a derived material, it is possible to provide an ultraviolet absorber using a material produced from a naturally derived raw material.
本発明の最良の実施形態を以下に説明する。
式（１）、(２)、(３)において、Ｒ1，Ｒ2，Ｒ7およびＲ8は水素原子、炭素数１〜４０、好ましくは１〜２０の直鎖状もしくは分岐状のアルキル基のいずれかを示す。炭素数１〜４０の直鎖状もしくは分岐状のアルキル基の具体例は、メチル、エチル、プロピル、ブチル、２−メチル−１−ブチル、２−エチル−１−ヘキシル、ラウリル、オクタデシル、エイコシル、イソプロピル、イソブチル、シクロヘキシル、イソノルボルニル、ｔ−ブチル、アダマンチルなどを挙げることができる。
The best embodiment of the present invention will be described below.
In the formulas (1), (2) and (3), R 1 , R 2 , R 7 and R 8 are a hydrogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms. Indicates one of the following. Specific examples of the linear or branched alkyl group having 1 to 40 carbon atoms include methyl, ethyl, propyl, butyl, 2-methyl-1-butyl, 2-ethyl-1-hexyl, lauryl, octadecyl, eicosyl, Examples include isopropyl, isobutyl, cyclohexyl, isonorbornyl, t-butyl, adamantyl and the like.
また、式（１）、(２)、(３)において、Ｒ3，Ｒ4，Ｒ6，Ｒ9およびＲ10は、水素原子、水酸基、炭素数１〜４０の直鎖状もしくは分岐状のアルコキシル基、アセチル基のいずれかを示す。炭素数１〜４０の直鎖状もしくは分岐状のアルコキシル基の具体例は、メトキシ、エトキシ、プロピルオキシ、ブチルオキシ、２−メチル−１−ブトキシ、２−エチル−１−ヘキシルオキシ、ラウリルオキシ、オクタデシルオキシ、エイコシルオキシ等の第一級アルコキシル基、イソプロピルオキシ、イソブトキシ、シクロヘキシルオキシ、イソノルボルニルオキシ等の第二級アルコキシル基、さらにはｔ−ブトキシ、アダマンチルオキシといった第三級アルコキシル基などを挙げることができる。 In the formulas (1), (2), and (3), R 3 , R 4 , R 6 , R 9 and R 10 are each a hydrogen atom, a hydroxyl group, a linear or branched group having 1 to 40 carbon atoms. It represents either an alkoxyl group or an acetyl group. Specific examples of the linear or branched alkoxyl group having 1 to 40 carbon atoms include methoxy, ethoxy, propyloxy, butyloxy, 2-methyl-1-butoxy, 2-ethyl-1-hexyloxy, lauryloxy, octadecyl Primary alkoxyl groups such as oxy and eicosyloxy, secondary alkoxyl groups such as isopropyloxy, isobutoxy, cyclohexyloxy, and isonorbornyloxy; and tertiary alkoxyl groups such as t-butoxy and adamantyloxy Can be mentioned.
式（１）、(２)、(３)において、Ｒ5およびＲ11は、アミノ基、水酸基、炭素数１〜４０の直鎖状、分岐状もしくは環状のアルコキシル基、アセチル基のいずれかを示す。アミノ基の具体例は、Ｎ,Ｎ−ジメチルアミノ基、Ｎ−メチルアミノ基など挙げられ、炭素数１〜４０の直鎖状もしくは分岐状のアルコキシル基の具体例は、上述したＲ3，Ｒ4，Ｒ6，Ｒ9およびＲ10の具体例として示したものと同一のものが挙げられる。 In the formulas (1), (2), and (3), R 5 and R 11 are any one of an amino group, a hydroxyl group, a linear, branched or cyclic alkoxyl group having 1 to 40 carbon atoms, and an acetyl group. Show. Specific examples of the amino group include N, N-dimethylamino group, N-methylamino group, and the like. Specific examples of the linear or branched alkoxyl group having 1 to 40 carbon atoms include R 3 and R described above. 4, R 6, R 9 and the same as those shown as specific examples of R 10 can be mentioned.
また式（１）、(２)、(３)において、Ｘは酸素原子またはＮＨを示す。 In the formulas (1), (2) and (3), X represents an oxygen atom or NH.
式（１）、（２）、（３）で示す化合物の具体例を以下に挙げるが、本実施形態にかかる芳香族化合物はこれらの化合物に限定されるものではない。尚、以下に示す芳香族化合物においてａ，ｂ，ｃ，ｄ，ｅ，ｈ，ｉ，ｊ，ｋ，ｍ，ｎは０〜４０の整数である。
式（１）、(２)、(３)に示す芳香族化合物の原料は桂皮酸誘導体であり、多くは天然中に存在する化合物である。具体例として、４−ヒドロキシ桂皮酸、コーヒー酸、フェルラ酸、シナピン酸などが挙げられる。また、前記桂皮酸誘導体は紫外線を吸収する部位である芳香環を有し、かつ非石油由来物質として安定供給可能な化合物群である。 The raw materials of the aromatic compounds represented by the formulas (1), (2) and (3) are cinnamic acid derivatives, and many are compounds existing in nature. Specific examples include 4-hydroxycinnamic acid, caffeic acid, ferulic acid, sinapinic acid and the like. The cinnamic acid derivatives are a group of compounds that have an aromatic ring that is a site that absorbs ultraviolet rays and can be stably supplied as non-petroleum-derived substances.
更に、前記桂皮酸誘導体は、カルボン酸、フェノール性の水酸基、二重結合など、それぞれ反応性の異なる官能基をその分子内に同時に有しているため、反応性の異なる各官能基ごとに、異なる性質を付与することができ、その機能や、融点、溶解性などの物性を比較的自由に設定可能であるという特徴を有する。 Furthermore, since the cinnamic acid derivative has functional groups having different reactivity, such as carboxylic acid, phenolic hydroxyl group and double bond, in the molecule at the same time, for each functional group having different reactivity, Different properties can be imparted, and the properties and physical properties such as melting point and solubility can be set relatively freely.
式（１）、（２）、（３）で示す芳香族化合物はこの桂皮酸誘導体から得られ、原料である桂皮酸誘導体より官能基の数が多くなっていることから、より物性や機能の制御が容易となる。 The aromatic compounds represented by the formulas (1), (2), and (3) are obtained from this cinnamic acid derivative and have a larger number of functional groups than the cinnamic acid derivative as a raw material. Control becomes easy.
こうした天然由来の桂皮酸の１つであるフェルラ酸およびその誘導体のフェルラ酸エステル類は、３２０ｎｍ付近に最大吸収を持ち、３６０ｎｍ付近にその吸収端を有する化合物である。このことから、これらの化合物は中波長のＵＶ−Ｂに対する天然の紫外線吸収剤として注目されてきた。 Ferulic acid, which is one of these naturally occurring cinnamic acids, and ferulic acid esters of derivatives thereof are compounds having a maximum absorption near 320 nm and an absorption edge near 360 nm. Therefore, these compounds have attracted attention as natural ultraviolet absorbers for medium wavelength UV-B.
本実施形態に係る式（１）、（２）、（３）に示す芳香族化合物は、これらフェルラ酸ならびにフェルラ酸エステル類と同様３２０ｎｍ付近にその最大吸収波長を有するが、その吸光度はフェルラ酸及びフェルラ酸誘導体より大きくなっており、またその吸収端は４００ｎｍ付近にまで達する。さらに鋭意検討することにより、その吸光度を最大限まで大きくするとともに、従来はほとんど存在しなかったような４５０ｎｍ付近の紫外線まで吸収可能な物質の開発に成功した。 The aromatic compounds represented by the formulas (1), (2), and (3) according to this embodiment have the maximum absorption wavelength in the vicinity of 320 nm, similar to these ferulic acid and ferulic acid esters, but the absorbance thereof is ferulic acid. In addition, the absorption edge is larger than that of the ferulic acid derivative, and the absorption edge reaches around 400 nm. Furthermore, through intensive studies, the inventors have succeeded in developing a substance capable of absorbing the ultraviolet light near 450 nm, which has been increased to the maximum, and has hardly existed in the past.
すなわち、有害な紫外線である長波長ＵＶ−Ａおよび中波長であるＵＶ−Ｂを同時に効率よく吸収する紫外線吸収剤の開発を行い、また、近年需要の高まっている４００ｎｍ以上の長波長領域の紫外線を効率的に吸収する材料の開発に成功したのである。 That is, the development of an ultraviolet absorber that efficiently absorbs harmful UV rays, such as long-wavelength UV-A and medium-wavelength UV-B, at the same time. We have succeeded in developing a material that efficiently absorbs water.
本実施形態に係る式（１）に示す芳香族化合物を製造する際には、例えば、前記桂皮酸誘導体を金属触媒の存在下溶媒中に分散し、所定時間還流を行った後、析出固体を濾別し、得られた溶液を減圧下で濃縮する。この濃縮により得られた残査を精製することにより第１中間生成物を得、該第１中間生成物を塩基性溶媒に溶解し、無水酢酸等の保護試薬を滴下し、その後室温で攪拌を行う。所定時間経過後加水し、塩酸などで酸性化し、有機溶媒で抽出、水洗を行う。得られた有機層を減圧蒸留することで第２中間生成物を得る。 When producing the aromatic compound represented by the formula (1) according to the present embodiment, for example, the cinnamic acid derivative is dispersed in a solvent in the presence of a metal catalyst, refluxed for a predetermined time, and then the precipitated solid is added. Filter off and concentrate the resulting solution under reduced pressure. By purifying the residue obtained by this concentration, a first intermediate product is obtained, the first intermediate product is dissolved in a basic solvent, a protective reagent such as acetic anhydride is added dropwise, and then stirred at room temperature. Do. Water is added after a predetermined time, acidified with hydrochloric acid, etc., extracted with an organic solvent, and washed with water. The obtained organic layer is distilled under reduced pressure to obtain a second intermediate product.
得られた第２中間生成物をＤＤＱなどの酸化剤とともに溶媒に溶解し、所定時間還流を行った後、析出した固体を濾別することで得られた溶液を減圧下で濃縮する。この濃縮により得られた残査を精製することにより目的生成物としての式（１）で示す芳香族化合物を得ることができる。 The obtained second intermediate product is dissolved in a solvent together with an oxidizing agent such as DDQ, refluxed for a predetermined time, and then the solution obtained by filtering the precipitated solid is concentrated under reduced pressure. By purifying the residue obtained by this concentration, the aromatic compound represented by the formula (1) as the target product can be obtained.
更に、上記方法により得られた式（１）で示す芳香族化合物について、該芳香族化合物の有する所定の官能基を他の官能基に置換する反応を行うことによって、式（１）で示す他の芳香族化合物を得ることができる。 Furthermore, the aromatic compound represented by the formula (1) obtained by the above method is subjected to a reaction for substituting a predetermined functional group possessed by the aromatic compound with another functional group. The aromatic compound can be obtained.
本実施形態に係る式（２）に示す芳香族化合物を製造方法は、上記方法により得られた式（１）に示す芳香族化合物を溶媒に溶解し、酸化剤を加え攪拌を行う。その後、溶媒を留去し、得られた残査を精製することにより目的生成物としての式（２）で示す芳香族化合物を得ることができる。 In the method for producing an aromatic compound represented by the formula (2) according to the present embodiment, the aromatic compound represented by the formula (1) obtained by the above method is dissolved in a solvent, and an oxidant is added and stirred. Then, the aromatic compound shown by Formula (2) as a target product can be obtained by distilling a solvent off and refine | purifying the obtained residue.
本実施形態に係る式（１）、（２）、（３）に示す芳香族化合物は、紫外線吸収剤としての利用が可能であり、太陽光や蛍光灯にさらされるような各種プラスチック（合成樹脂）に所定量混合することで、広い波長範囲の紫外線を吸収可能となり、該プラスチックの劣化などを抑止可能である。具体的には、ガラス代替用の透明プラスチック、もしくはそのコーティング剤、内外装用の樹脂、または包装用フィルムなどに本実施形態に係る式（１）、（２）、（３）に示す芳香族化合物を所定量混合することなどを挙げることができる。 The aromatic compounds represented by the formulas (1), (2), and (3) according to this embodiment can be used as ultraviolet absorbers, and can be used as various plastics (synthetic resins) that are exposed to sunlight or fluorescent lamps. ) Can absorb ultraviolet rays in a wide wavelength range, and the deterioration of the plastic can be suppressed. Specifically, the aromatic compound represented by the formulas (1), (2), and (3) according to the present embodiment is used for a transparent plastic for glass replacement, or a coating agent thereof, a resin for interior and exterior, or a packaging film. And the like in a predetermined amount.
また、本実施形態に係る式（１）、（２）、（３）に示す芳香族化合物は、近年需要の増えている配線基盤の積層化に伴う裏写り防止剤（光遮蔽剤）としての用途も期待できる。 In addition, the aromatic compounds represented by the formulas (1), (2), and (3) according to the present embodiment are used as anti-show-through agents (light shielding agents) associated with the lamination of wiring boards, which have been increasing in demand in recent years. Applications can also be expected.
以下の実施例は本発明の内容を詳細に説明しているが、これらは本発明の内容を制限するものではない。 The following examples illustrate the contents of the present invention in detail, but these do not limit the contents of the present invention.
下記化学式（４）で表される芳香族化合物の合成。
この第１中間生成物０．５ｇをピリジン10ｍＬに溶解し、無水酢酸2ｍＬを滴下した後室温で攪拌を行った。２時間後水100ｍＬを加え、さらに６Ｎ−ＨＣｌで酸性化した後酢酸エチルで抽出、水洗を行った。得られた有機層を硫酸マグネシウムで乾燥させた後、減圧蒸留することで第２中間生成物０．５５ｇを得た。 0.5 g of this first intermediate product was dissolved in 10 mL of pyridine, and 2 mL of acetic anhydride was added dropwise, followed by stirring at room temperature. Two hours later, 100 mL of water was added, and the mixture was further acidified with 6N-HCl, extracted with ethyl acetate, and washed with water. The obtained organic layer was dried over magnesium sulfate and then distilled under reduced pressure to obtain 0.55 g of a second intermediate product.
得られた第２中間生成物０．５ｇおよびＤＤＱ０．３ｇをジオキサン１００ｍＬに溶解し、２０時間還流した。室温まで戻した後に析出固体を濾別し、得られた溶液を減圧下で濃縮した。得られた残査をシリカゲルカラムクロマトグラフィーで精製することにより目的生成物としての式（４）に示す芳香族化合物０．３ｇを得た。得られた芳香族化合物のスペクトルデータは次の通りである。
1H NMR（400MHz, CDCl3）δ 7.84 (1H, d, J=2.0 Hz), 7.81 (1H, d, J=16.0 Hz), 7.79 (1H, d, J=1.2 Hz), 7.68 (1H, dd, J=2.0, 8.4 Hz), 7.15 (1H, d, J=8.4 Hz), 7.03 (1H, d, J=1.2 Hz), 6.47 (1H, d, J=16.0 Hz), 4.05 (3H, s), 3.96 (3H, s), 3.94 (3H, s), 3.84 (3H, s), 2.35 (3H, s); 13C NMR (100MHz, CDCl3) δ 168.62, 167.42, 163.97, 160.61, 150.75, 145.36, 145.33, 144.25, 141.57, 131.56, 129.06, 127.63, 122.61, 122.41, 117.22, 116.19, 113.82, 109.24, 106.100, 56.12, 51.86, 51.72, 20.68
0.5 g of the obtained second intermediate product and 0.3 g of DDQ were dissolved in 100 mL of dioxane and refluxed for 20 hours. After returning to room temperature, the precipitated solid was filtered off, and the resulting solution was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 0.3 g of an aromatic compound represented by the formula (4) as a target product. The spectrum data of the obtained aromatic compound are as follows.
1 H NMR (400 MHz, CDCl 3 ) δ 7.84 (1H, d, J = 2.0 Hz), 7.81 (1H, d, J = 16.0 Hz), 7.79 (1H, d, J = 1.2 Hz), 7.68 (1H, dd, J = 2.0, 8.4 Hz), 7.15 (1H, d, J = 8.4 Hz), 7.03 (1H, d, J = 1.2 Hz), 6.47 (1H, d, J = 16.0 Hz), 4.05 (3H, s), 3.96 (3H, s), 3.94 (3H, s), 3.84 (3H, s), 2.35 (3H, s); 13 C NMR (100 MHz, CDCl 3 ) δ 168.62, 167.42, 163.97, 160.61, 150.75 , 145.36, 145.33, 144.25, 141.57, 131.56, 129.06, 127.63, 122.61, 122.41, 117.22, 116.19, 113.82, 109.24, 106.100, 56.12, 51.86, 51.72, 20.68
下記化学式（５）で表される芳香族化合物の合成。
フェルラ酸メチルに替えて、フェルラ酸エチルを原料に用いた以外は上記実施例１と同様に反応を行い、目的生成物としての式（５）に示す芳香族化合物を得た。得られた芳香族化合物のスペクトルデータは次の通りである。
1H NMR（400MHz, CDCl3）δ 7.83-7.81 (2H, m), 7.80 (1H, d, J=16.0 Hz), 7.68 (1H, dd, J=2.0, 8.4 Hz), 7.15 (1H, d, J=8.4 Hz), 7.05 (1H, d, J=1.6 Hz), 6.46 (1H, d, J=16.0 Hz), 4.44 (2H, q, 7.2 Hz), 4.30 (2H, q, 7.2 Hz), 4.06 (3H, s), 3.93 (3H, s), 2.35 (3H, s), 1.44 (3H, t, 7.2 Hz), 1.37 (3H, t, 7.2 Hz); 13C NMR (100MHz, CDCl3) δ 168.65, 167.05, 163.57, 160.53, 150.75, 145.35, 145.18, 144.29, 141.54, 131.62, 129.18, 127.76, 122.57, 122.52, 117.66, 116.32, 113.85, 109.56, 105.96, 60.98, 60.54, 56.14, 20.70, 14.36
The reaction was carried out in the same manner as in Example 1 except that ethyl ferulate was used as a raw material instead of methyl ferulate to obtain an aromatic compound represented by the formula (5) as a target product. The spectrum data of the obtained aromatic compound are as follows.
1 H NMR (400 MHz, CDCl 3 ) δ 7.83-7.81 (2H, m), 7.80 (1H, d, J = 16.0 Hz), 7.68 (1H, dd, J = 2.0, 8.4 Hz), 7.15 (1H, d , J = 8.4 Hz), 7.05 (1H, d, J = 1.6 Hz), 6.46 (1H, d, J = 16.0 Hz), 4.44 (2H, q, 7.2 Hz), 4.30 (2H, q, 7.2 Hz) , 4.06 (3H, s), 3.93 (3H, s), 2.35 (3H, s), 1.44 (3H, t, 7.2 Hz), 1.37 (3H, t, 7.2 Hz); 13 C NMR (100 MHz, CDCl 3 ) δ 168.65, 167.05, 163.57, 160.53, 150.75, 145.35, 145.18, 144.29, 141.54, 131.62, 129.18, 127.76, 122.57, 122.52, 117.66, 116.32, 113.85, 109.56, 105.96, 60.98, 60.54, 56.14, 20.70, 14.
下記化学式（６）で表される芳香族化合物の合成。
上記実施例１で得られた芳香族化合物０．２ｇをピロリジン２ｍＬに溶解し、そのまま５分間攪拌を行った。その後水１０ｍＬを加え、１Ｎ−ＨＣｌで中和した後、析出固体を濾別乾燥し、目的生成物として式（６）に示す芳香族化合物０．１８ｇを得た。得られた芳香族化合物のスペクトルデータは次の通りである。
1H NMR（400MHz, CDCl3）δ 7.81 (1H, d, J=16.0 Hz), 7.78 (1H, d, J=1.2 Hz), 7.76 (1H, d, J=2.0 Hz), 7.66 (1H, dd, J=2.0, 8.4 Hz), 7.03-7.00 (2H, m), 6.46(1H, d, J=16.0 Hz), 5.99 (1H, s), 4.05 (3H, s), 3.99 (3H, s), 3.96 (3H, s), 3.84 (3H, s); 13C NMR (100MHz, CDCl3) δ 167.50, 164.28, 161.87, 148.01, 145.99, 145.52, 145.19, 143.98, 131.36, 129.29, 123.79, 121.04, 117.02, 116.14, 114.20, 112.12, 107.83, 105.79, 56.16, 56.09, 51.74, 51.72
0.2 g of the aromatic compound obtained in Example 1 was dissolved in 2 mL of pyrrolidine and stirred as it was for 5 minutes. Thereafter, 10 mL of water was added and neutralized with 1N-HCl, and then the precipitated solid was filtered and dried to obtain 0.18 g of an aromatic compound represented by the formula (6) as a target product. The spectrum data of the obtained aromatic compound are as follows.
1 H NMR (400 MHz, CDCl 3 ) δ 7.81 (1H, d, J = 16.0 Hz), 7.78 (1H, d, J = 1.2 Hz), 7.76 (1H, d, J = 2.0 Hz), 7.66 (1H, dd, J = 2.0, 8.4 Hz), 7.03-7.00 (2H, m), 6.46 (1H, d, J = 16.0 Hz), 5.99 (1H, s), 4.05 (3H, s), 3.99 (3H, s ), 3.96 (3H, s), 3.84 (3H, s); 13 C NMR (100 MHz, CDCl 3 ) δ 167.50, 164.28, 161.87, 148.01, 145.99, 145.52, 145.19, 143.98, 131.36, 129.29, 123.79, 121.04, 117.02, 116.14, 114.20, 112.12, 107.83, 105.79, 56.16, 56.09, 51.74, 51.72
下記化学式（７）で表される芳香族化合物の合成。
実施例２で得られた化合物を原料とした以外は上記実施例３と同様に反応を行い、目的生成物である式（７）に示す芳香族化合物を得た。得られた芳香族化合物のスペクトルデータは次の通りである。
1H NMR（400MHz, CDCl3）δ 7.80 (1H, d, J=16.0 Hz), 7.80 (1H, d, J=1.2 Hz), 7.74 (1H, d, J=2.0 Hz), 7.66 (1H, dd, J =2.0, 8.4 Hz), 7.02(1H, d, J =1.2 Hz), 7.01(1H, d, J=8.4 Hz), 6.45(1H, d, J=16.0 Hz), 5.95 (1H, s), 4.43 (2H, q, 7.2 Hz), 4.30 (2H, q, 7.2 Hz), 4.05 (3H, s), 3.99 (3H, s), 1.45 (3H, t, 7.2 Hz), 1.37 (3H, t, 7.2 Hz); 13C NMR (100MHz, CDCl3) δ 167.11, 163.88, 161.78, 147.96, 145.98, 145.33, 145.22, 144.01, 131.42, 129.42, 123.90, 121.17, 117.46, 116.29, 114.15, 112.13, 108.15, 105.65, 60.81, 60.53, 56.19, 56.11, 14.42, 14.38
A reaction was carried out in the same manner as in Example 3 except that the compound obtained in Example 2 was used as a raw material to obtain an aromatic compound represented by the formula (7), which was the target product. The spectrum data of the obtained aromatic compound are as follows.
1 H NMR (400 MHz, CDCl 3 ) δ 7.80 (1H, d, J = 16.0 Hz), 7.80 (1H, d, J = 1.2 Hz), 7.74 (1H, d, J = 2.0 Hz), 7.66 (1H, dd, J = 2.0, 8.4 Hz), 7.02 (1H, d, J = 1.2 Hz), 7.01 (1H, d, J = 8.4 Hz), 6.45 (1H, d, J = 16.0 Hz), 5.95 (1H, s), 4.43 (2H, q, 7.2 Hz), 4.30 (2H, q, 7.2 Hz), 4.05 (3H, s), 3.99 (3H, s), 1.45 (3H, t, 7.2 Hz), 1.37 (3H , t, 7.2 Hz); 13 C NMR (100 MHz, CDCl 3 ) δ 167.11, 163.88, 161.78, 147.96, 145.98, 145.33, 145.22, 144.01, 131.42, 129.42, 123.90, 121.17, 117.46, 116.29, 114.15, 112.13, 108.15 , 105.65, 60.81, 60.53, 56.19, 56.11, 14.42, 14.38
下記化学式（８）で表される化合物の合成。
フェルラ酸メチルに替えて、フェルラ酸２−メチル−１−ブタノールを用いた以外は上記実施例１と同様に反応を行い中間生成物を得た後、その中間生成物を原料として実施例３と同様の反応を行い、目的生成物を得た。得られた式（８）に示す芳香族化合物のスペクトルデータは次の通りである。
1H NMR（400MHz, CDCl3）δ 7.84 (1H, d, J=1.2 Hz), 7.78 (1H, d, J=16.0 Hz), 7.73 (1H, d, J=2.0 Hz), 7.65 (1H, dd, J=8.4, 2.0 Hz), 7.02-7.00 (2H, m), 6.46 (1H, d, J=16.0 Hz), 5.96 (1H, s), 4.29-4.02 (4H, m), 4.06 (3H, s), 3.99 (3H, s), 1.92-0.94 (18H, m); 13C NMR (100MHz, CDCl3) δ 167.21, 164.04, 161.91, 147.94, 145.97, 145.21, 143.98, 131.45, 129.40, 123.91, 121.18, 117.52, 116.00, 114.14, 112.16, 108.24, 105.90, 69.55, 69.17, 56.17, 56.13, 34.27, 34.26, 26.23, 26.10, 16.62, 16.45, 11.26, 11.23
The reaction was conducted in the same manner as in Example 1 except that 2-methyl-1-butanol of ferulic acid was used instead of methyl ferulate to obtain an intermediate product, and then the intermediate product was used as a raw material in Example 3. The same reaction was performed to obtain the desired product. The spectrum data of the obtained aromatic compound represented by the formula (8) is as follows.
1 H NMR (400 MHz, CDCl 3 ) δ 7.84 (1H, d, J = 1.2 Hz), 7.78 (1H, d, J = 16.0 Hz), 7.73 (1H, d, J = 2.0 Hz), 7.65 (1H, dd, J = 8.4, 2.0 Hz), 7.02-7.00 (2H, m), 6.46 (1H, d, J = 16.0 Hz), 5.96 (1H, s), 4.29-4.02 (4H, m), 4.06 (3H , s), 3.99 (3H, s), 1.92-0.94 (18H, m); 13 C NMR (100MHz, CDCl 3 ) δ 167.21, 164.04, 161.91, 147.94, 145.97, 145.21, 143.98, 131.45, 129.40, 123.91, 121.18, 117.52, 116.00, 114.14, 112.16, 108.24, 105.90, 69.55, 69.17, 56.17, 56.13, 34.27, 34.26, 26.23, 26.10, 16.62, 16.45, 11.26, 11.23
下記化学式（９）で表される化合物の合成。
実施例３で得られた芳香族化合物１００ｍｇをＴＨＦ１ｍＬに溶解し、そこに水酸化ナトリウム１００ｍｇを水１０ｍＬに溶解した溶液を加え、室温で８時間攪拌を行った。その後１Ｎ−ＨＣｌで中和し、析出固体を濾別乾燥することにより、目的物８０ｍｇを得た。得られた式（９）に示す芳香族化合物のスペクトルデータは次の通りである。
1H NMR（400MHz, DMSO-d6）δ 7.77 (1H, d, J=1.2 Hz), 7.72 (1H, d, J=16.0 Hz), 7.69 (1H, d, J=2.0 Hz), 7.49 (1H, dd, J=2.0, 8.4 Hz), 7.42(1H, d, J=1.2 Hz), 6.93 (1H, d, J=8.4 Hz), 6.63 (1H, d, J=16.0 Hz), 4.03 (3H, s), 3.90 (3H, s), 3.85 (3H, s); 13C NMR (100MHz, DMSO-d6) δ 167.70, 163.55, 161.07, 149.41,147.12, 144.96, 144.49, 143.06, 131.65, 128.61, 122.92, 119.37, 118.85, 115.55, 115.33, 113.27, 107.02, 106.36, 56.17, 51.77
100 mg of the aromatic compound obtained in Example 3 was dissolved in 1 mL of THF, and a solution obtained by dissolving 100 mg of sodium hydroxide in 10 mL of water was added thereto, followed by stirring at room temperature for 8 hours. Thereafter, the mixture was neutralized with 1N-HCl, and the precipitated solid was separated by filtration and dried to obtain 80 mg of the desired product. The spectrum data of the obtained aromatic compound represented by the formula (9) is as follows.
1 H NMR (400MHz, DMSO-d 6 ) δ 7.77 (1H, d, J = 1.2 Hz), 7.72 (1H, d, J = 16.0 Hz), 7.69 (1H, d, J = 2.0 Hz), 7.49 ( 1H, dd, J = 2.0, 8.4 Hz), 7.42 (1H, d, J = 1.2 Hz), 6.93 (1H, d, J = 8.4 Hz), 6.63 (1H, d, J = 16.0 Hz), 4.03 ( 3H, s), 3.90 (3H, s), 3.85 (3H, s); 13 C NMR (100MHz, DMSO-d 6 ) δ 167.70, 163.55, 161.07, 149.41,147.12, 144.96, 144.49, 143.06, 131.65, 128.61 , 122.92, 119.37, 118.85, 115.55, 115.33, 113.27, 107.02, 106.36, 56.17, 51.77
下記化学式（１０）で表される化合物の合成。
実施例３で得られた化合物１００ｍｇをＴＨＦ１ｍＬに溶解し、そこに水酸化ナトリウム１００ｍｇを水１０ｍＬに溶解した溶液を加え、乾留下８時間攪拌を行った。その後１Ｎ−ＨＣｌで中和し、析出固体を濾別乾燥することにより、目的物７０ｍｇを得た。
得られた式（１９）に示す芳香族化合物のスペクトルデータは次の通りである。
1H NMR（400MHz, DMSO-d6）δ 7.76 (1H, d, J=1.2 Hz), 7.72 (1H, d, J=2.0 Hz), 7.69 (1H, d, J =16.0 Hz), 7.49 (1H, dd, J =2.0, 8.4 Hz), 7.40(1H, d, J =1.2 Hz), 6.92(1H, d, J=8.4 Hz), 6.59(1H, d, J=16.0 Hz), 4.03 (3H, s), 3.84 (3H, s); 13C NMR (100MHz, DMSO-d6) δ 167.82, 164.84, 160.83, 149.34, 147.20, 145.12, 144.74, 143.24, 131.60, 129.41, 123.06, 119.83, 118.88, 115.74, 115.44, 113.58, 108.20, 106.38, 56.34, 55.87
100 mg of the compound obtained in Example 3 was dissolved in 1 mL of THF, and a solution obtained by dissolving 100 mg of sodium hydroxide in 10 mL of water was added thereto, followed by stirring for 8 hours under dry distillation. Thereafter, the mixture was neutralized with 1N-HCl, and the precipitated solid was separated by filtration and dried to obtain 70 mg of the desired product.
The spectrum data of the obtained aromatic compound represented by the formula (19) is as follows.
1 H NMR (400MHz, DMSO-d 6 ) δ 7.76 (1H, d, J = 1.2 Hz), 7.72 (1H, d, J = 2.0 Hz), 7.69 (1H, d, J = 16.0 Hz), 7.49 ( 1H, dd, J = 2.0, 8.4 Hz), 7.40 (1H, d, J = 1.2 Hz), 6.92 (1H, d, J = 8.4 Hz), 6.59 (1H, d, J = 16.0 Hz), 4.03 ( 3H, s), 3.84 (3H, s); 13 C NMR (100 MHz, DMSO-d 6 ) δ 167.82, 164.84, 160.83, 149.34, 147.20, 145.12, 144.74, 143.24, 131.60, 129.41, 123.06, 119.83, 118.88, 115.74, 115.44, 113.58, 108.20, 106.38, 56.34, 55.87
下記化学式（１１）で表される化合物の合成。
実施例７で得られた化合物１５０ｍｇをメタノール２５ｍＬに分散させ、そこに硫酸を４滴加えて５０度で３時間攪拌した。室温に戻した後減圧下で濃縮を行い、得られた残渣をシリカゲルカラムクロマトグラフィーで精製することにより目的物１０２ｍｇを得た。得られた式（１１）に示す芳香族化合物のスペクトルデータは次の通りである。
1H NMR（400MHz, DMSO-d6）δ 7.79-7.75 (2H, m), 7.73 (1H, d, J=2.0 Hz), 7.50 (1H, dd, J=2.0, 8.4 Hz), 7.44 (1H, d, J=1.2 Hz), 6.92 (1H, d, J=8.4 Hz), 6.70 (1H, d, J=16.0 Hz), 4.03 (3H, s), 3.84 (3H, s), 3.75 (3H, s); 13C NMR (100MHz, DMSO-d6) δ 166.93, 164.85, 160.71, 149.32, 147.20, 145.39, 145.13, 143.36, 131.33, 129.47, 123.03, 119.83, 117.43, 116.19, 115.44, 113.56, 108.35, 106.34, 56.35, 55.86, 51.64, 30.88
150 mg of the compound obtained in Example 7 was dispersed in 25 mL of methanol, 4 drops of sulfuric acid was added thereto, and the mixture was stirred at 50 degrees for 3 hours. After returning to room temperature, concentration was performed under reduced pressure, and the obtained residue was purified by silica gel column chromatography to obtain 102 mg of the desired product. The spectrum data of the obtained aromatic compound represented by the formula (11) is as follows.
1 H NMR (400MHz, DMSO-d 6 ) δ 7.79-7.75 (2H, m), 7.73 (1H, d, J = 2.0 Hz), 7.50 (1H, dd, J = 2.0, 8.4 Hz), 7.44 (1H , d, J = 1.2 Hz), 6.92 (1H, d, J = 8.4 Hz), 6.70 (1H, d, J = 16.0 Hz), 4.03 (3H, s), 3.84 (3H, s), 3.75 (3H , s); 13 C NMR (100 MHz, DMSO-d 6 ) δ 166.93, 164.85, 160.71, 149.32, 147.20, 145.39, 145.13, 143.36, 131.33, 129.47, 123.03, 119.83, 117.43, 116.19, 115.44, 113.56, 108.35, 106.34, 56.35, 55.86, 51.64, 30.88
下記化学式で表される化合物の合成。
メタノールに替えてＣ12Ｈ25ＯＨを用いた以外は上記実施例８と同様に試験を行い目的生成物を得た。得られた式（１２）に示す芳香族化合物のスペクトルデータは次の通りである。
1H NMR（400MHz, CDCl3）δ 7.75 (1H, d, J=16.0 Hz), 7.41 (1H, dd, J=2.0, 8.4 Hz), 7.37 (1H, d, J=2.0 Hz), 7.33 (1H, d, J=1.2 Hz), 6.99 (1H, d, J=8.4 Hz), 6.97 (1H, d, J=1.2 Hz), 6.87 (1H, s), 6.42 (1H, d, J=16.0 Hz), 5.78 (1H, s), 4.22 (2H, t, J=6.8 Hz), 4.07 (3H, s), 4.01 (3H, s), 1.75-0.86 (22H, m); 13C NMR (100MHz, CDCl3) δ 167.28, 157.33, 146.73, 146.61, 145.33, 145.29, 145.09, 131.42, 130.57, 122.48, 119.03, 116.95, 114.80, 114.48, 107.59, 105.06, 100.14, 64.70, 56.17, 56.08, 31.92, 29.66, 29.64, 29.60, 29.55, 29.35, 29.31, 28.78, 26.01, 22.69, 14.12
A test was conducted in the same manner as in Example 8 except that C 12 H 25 OH was used instead of methanol to obtain the desired product. The spectrum data of the obtained aromatic compound represented by the formula (12) is as follows.
1 H NMR (400 MHz, CDCl 3 ) δ 7.75 (1H, d, J = 16.0 Hz), 7.41 (1H, dd, J = 2.0, 8.4 Hz), 7.37 (1H, d, J = 2.0 Hz), 7.33 ( 1H, d, J = 1.2 Hz), 6.99 (1H, d, J = 8.4 Hz), 6.97 (1H, d, J = 1.2 Hz), 6.87 (1H, s), 6.42 (1H, d, J = 16.0 Hz), 5.78 (1H, s), 4.22 (2H, t, J = 6.8 Hz), 4.07 (3H, s), 4.01 (3H, s), 1.75-0.86 (22H, m); 13 C NMR (100 MHz , CDCl 3 ) δ 167.28, 157.33, 146.73, 146.61, 145.33, 145.29, 145.09, 131.42, 130.57, 122.48, 119.03, 116.95, 114.80, 114.48, 107.59, 105.06, 100.14, 64.70, 56.17, 56.08, 31.92.29, 66. , 29.60, 29.55, 29.35, 29.31, 28.78, 26.01, 22.69, 14.12
下記化学式（１３）で表される化合物の合成。
実施例７で得られた化合物２００ｍｇを０．５Ｎ−ＮａＯＨ水溶液３．５ｍＬに溶解し、さらに水を加えてトータル１０ｍＬにした。そこに氷冷下無水酢酸１００μＬ加えたのち１０分、さらに室温で８０分攪拌を行った。その後、水を２５ｍＬ加えた後６Ｎ−ＨＣｌで中和し、析出固体を濾別乾燥させることにより目的生成物１６２ｍｇを得た。得られた式（１３）に示す芳香族化合物のスペクトルデータは次の通りである。
1H NMR（400MHz, DMSO-d6）δ 7.83 (1H, d, J=2.0 Hz), 7.80 (1H, d, J=1.2 Hz), 7.71 (1H, d, J=15.6 Hz), 7.57 (1H, dd, J=2.0, 8.4 Hz), 7.45 (1H, d, J=1.2 Hz), 7.27 (1H, d, J=8.4 Hz), 6.61 (1H, d, J=15.6 Hz), 4.04 (3H, s), 3.85 (3H, s), 2.31 (3H, s)
200 mg of the compound obtained in Example 7 was dissolved in 3.5 mL of 0.5N NaOH aqueous solution, and water was further added to make a total of 10 mL. The mixture was added with 100 μL of acetic anhydride under ice-cooling, and stirred for 10 minutes and further at room temperature for 80 minutes. Then, 25 mL of water was added and neutralized with 6N-HCl, and the precipitated solid was filtered and dried to obtain 162 mg of the desired product. The spectrum data of the obtained aromatic compound represented by the formula (13) is as follows.
1 H NMR (400MHz, DMSO-d 6 ) δ 7.83 (1H, d, J = 2.0 Hz), 7.80 (1H, d, J = 1.2 Hz), 7.71 (1H, d, J = 15.6 Hz), 7.57 ( 1H, dd, J = 2.0, 8.4 Hz), 7.45 (1H, d, J = 1.2 Hz), 7.27 (1H, d, J = 8.4 Hz), 6.61 (1H, d, J = 15.6 Hz), 4.04 ( 3H, s), 3.85 (3H, s), 2.31 (3H, s)
下記化学式（１４）で表される化合物の合成。
実施例１０で得られた芳香族化合物が８９ｍｇと、Ｃ12Ｈ25ＯＨが１７０ｍｇと、トリフェニルホスフィンが２６０ｍｇとをジクロロメタン１０ｍＬ中に分散させ、そこにアゾジイソプロピルジカルボキシレートの４０％トルエン溶液を５００ｍｇ滴下した後一晩室温で攪拌を行った。その後減圧下で濃縮を行い、得られた残渣をシリカゲルカラムクロマトグラフィーで精製することにより目的生成物を７０ｍｇを得た。得られた式（１４）に示す芳香族化合物のスペクトルデータは次の通りである。
1H NMR（400MHz, CDCl3）δ 7.82 (1H, d, J=1.2 Hz), 7.82 (1H, d, J=2.0 Hz), 7.79 (1H, d, J=16.0 Hz), 7.67 (1H, dd, J=2.0, 8.4 Hz), 7.14 (1H, d, J=8.4 Hz), 7.05 (1H, d, J=1.2 Hz), 6.46 (1H, d, J=16.0 Hz), 4.36 (2H, t, J=6.8 Hz), 4.23 (2H, t, J=6.8 Hz), 4.06 (3H, s), 3.93 (3H, s), 2.35 (3H, s), 1.83-0.87 (46H, m)
89 mg of the aromatic compound obtained in Example 10, 170 mg of C 12 H 25 OH, and 260 mg of triphenylphosphine were dispersed in 10 mL of dichloromethane, and a 40% toluene solution of azodiisopropyldicarboxylate was added thereto. After adding 500 mg dropwise, the mixture was stirred overnight at room temperature. Thereafter, concentration was performed under reduced pressure, and the obtained residue was purified by silica gel column chromatography to obtain 70 mg of the desired product. The spectrum data of the obtained aromatic compound represented by the formula (14) is as follows.
1 H NMR (400 MHz, CDCl 3 ) δ 7.82 (1H, d, J = 1.2 Hz), 7.82 (1H, d, J = 2.0 Hz), 7.79 (1H, d, J = 16.0 Hz), 7.67 (1H, dd, J = 2.0, 8.4 Hz), 7.14 (1H, d, J = 8.4 Hz), 7.05 (1H, d, J = 1.2 Hz), 6.46 (1H, d, J = 16.0 Hz), 4.36 (2H, t, J = 6.8 Hz), 4.23 (2H, t, J = 6.8 Hz), 4.06 (3H, s), 3.93 (3H, s), 2.35 (3H, s), 1.83-0.87 (46H, m)
下記化学式（１５）で表される化合物の合成。
実施例７で得られた化合物５０ｍｇ、Ｃ20Ｈ41ＯＨを１５５ｍｇ、さらにトリフェニルホスフィン１４０ｍｇをジクロロメタン１５ｍＬ中に分散させ、そこにアゾジイソプロピルジカルボキシレートの４０％トルエン溶液を２６５ｍｇ滴下した後一晩室温で攪拌を行った。その後減圧下で濃縮を行い、得られた残渣にアセトン５０ｍＬを加え、析出固体を濾別乾燥することにより目的生成物１５３ｍｇを得た。得られた式（１５）に示す芳香族化合物のスペクトルデータは次の通りである。 50 mg of the compound obtained in Example 7, 155 mg of C 20 H 41 OH, and 140 mg of triphenylphosphine were dispersed in 15 mL of dichloromethane, and 265 mg of a 40% toluene solution of azodiisopropyldicarboxylate was added dropwise thereto overnight. Stir at room temperature. Thereafter, concentration was performed under reduced pressure, 50 mL of acetone was added to the obtained residue, and the precipitated solid was separated by filtration and dried to obtain 153 mg of the desired product. The spectrum data of the obtained aromatic compound represented by the formula (15) is as follows.
下記化学式（１６）で表される化合物の合成。
Ｃ20Ｈ41ＯＨに替えて２-エチル-１-ヘキサノールを用いた以外は上記実施例１２と同様に反応を行うことによって目的生成物を得た。得られた式（１６）に示す芳香族化合物のスペクトルデータは次の通りである。
1H NMR（400MHz, CDCl3）δ 7.85 (1H, d, J=1.2 Hz), 7.77 (1H, d, J=16.0 Hz), 7.68-7.66 (2H, m), 7.02 (1H, d, J=1.2 Hz), 6.95 (1H, d, J=9.2 Hz), 6.46 (1H, d, J=16.0 Hz), 4.32-3.93 (6H, m), 4.06 (3H, s), 3.94 (3H, s), 1.89-0.88 (45H, m); 13C NMR (100MHz, CDCl3) δ 167.27, 164.13, 162.06, 151.16, 148.93, 145.22, 145.15, 144.02, 131.45, 129.45, 123.36, 121.38, 117.59, 115.81, 113.37, 112.04, 108.32, 106.07, 76.30, 71.80, 67.14, 66.89, 56.36, 56.16, 39.03, 38.91, 30.57, 30.47, 30.39, 28.98, 23.97, 23.85, 23.75, 23.05, 23.01, 22.96, 14.08, 14.04, 11.05, 11.04, 10.95
The target product was obtained by carrying out the reaction in the same manner as in Example 12 except that 2-ethyl-1-hexanol was used instead of C 20 H 41 OH. The spectrum data of the obtained aromatic compound represented by the formula (16) is as follows.
1 H NMR (400 MHz, CDCl 3 ) δ 7.85 (1H, d, J = 1.2 Hz), 7.77 (1H, d, J = 16.0 Hz), 7.68-7.66 (2H, m), 7.02 (1H, d, J = 1.2 Hz), 6.95 (1H, d, J = 9.2 Hz), 6.46 (1H, d, J = 16.0 Hz), 4.32-3.93 (6H, m), 4.06 (3H, s), 3.94 (3H, s ), 1.89-0.88 (45H, m); 13 C NMR (100 MHz, CDCl 3 ) δ 167.27, 164.13, 162.06, 151.16, 148.93, 145.22, 145.15, 144.02, 131.45, 129.45, 123.36, 121.38, 117.59, 115.81, 113.37 , 112.04, 108.32, 106.07, 76.30, 71.80, 67.14, 66.89, 56.36, 56.16, 39.03, 38.91, 30.57, 30.47, 30.39, 28.98, 23.97, 23.85, 23.75, 23.05, 23.01, 22.96, 14.08, 14.04, 11.05, 11.04 , 10.95
下記化学式（１７）で表される化合物の合成。
1H NMR（400MHz, CDCl3）δ 7.82 (1H, d, J=16.0 Hz), 7.80 (1H, d, J=1.2 Hz), 7.74-7.71 (2H, m), 7.02 (1H, d, J=1.2 Hz), 6.97 (1H, d, J=9.2 Hz), 6.47 (1H, d, J=16.0 Hz), 4.06 (3H, s), 3.98 (3H, s), 3.97 (3H, s), 3.96 (3H, s), 3.84 (3H, s) ; 13C NMR (100MHz, CDCl3) δ 167.50, 164.26, 161.82, 151.08, 148.41, 145.51, 145.24, 144.08, 131.42, 129.29, 123.21, 121.54, 117.08, 116.16, 112.48, 110.51, 108.08, 105.84, 56.12, 56.09, 55.97, 51.78, 51.74
Synthesis of a compound represented by the following chemical formula (17).
1 H NMR (400MHz, CDCl 3 ) δ 7.82 (1H, d, J = 16.0 Hz), 7.80 (1H, d, J = 1.2 Hz), 7.74-7.71 (2H, m), 7.02 (1H, d, J = 1.2 Hz), 6.97 (1H, d, J = 9.2 Hz), 6.47 (1H, d, J = 16.0 Hz), 4.06 (3H, s), 3.98 (3H, s), 3.97 (3H, s), 3.96 (3H, s), 3.84 (3H, s); 13 C NMR (100 MHz, CDCl 3 ) δ 167.50, 164.26, 161.82, 151.08, 148.41, 145.51, 145.24, 144.08, 131.42, 129.29, 123.21, 121.54, 117.08, 116.16, 112.48, 110.51, 108.08, 105.84, 56.12, 56.09, 55.97, 51.78, 51.74
下記化学式（１８）で表される化合物の合成。
Ｃ20Ｈ41ＯＨに替えてエタノールを用いた以外は上記実施例１２と同様に反応を行うことによって目的生成物を得た。得られた式（１８）に示す芳香族化合物のスペクトルデータは次の通りである。 The target product was obtained by carrying out the reaction in the same manner as in Example 12 except that ethanol was used instead of C 20 H 41 OH. The spectrum data of the obtained aromatic compound represented by the formula (18) is as follows.
下記化学式（１９）で表される化合物の合成。
Ｃ20Ｈ41ＯＨに替えてＣ12Ｈ25ＯＨを用いた以外は上記実施例１２と同様に反応を行うことによって目的生成物を得た。得られた式（１９）に示す芳香族化合物のスペクトルデータは次の通りである。
1H NMR（400MHz, CDCl3）δ 7.82 (1H, d, J=1.2 Hz), 7.79 (1H, d, J=15.6 Hz), 7.69-7.67 (2H, m), 7.02 (1H, d, J=1.2 Hz), 6.95 (1H, d, J=9.2 Hz), 6.45 (1H, d, J=15.6 Hz), 4.36 (2H, t, J=6.8 Hz), 4.22 (2H, t, J=6.8 Hz), 4.09 (2H, t, J=6.8 Hz), 4.06 (3H, s), 3.96 (3H, s), 1.90-0.86 (69H, m)
The target product was obtained by carrying out the reaction in the same manner as in Example 12 except that C 12 H 25 OH was used instead of C 20 H 41 OH. The spectrum data of the obtained aromatic compound represented by the formula (19) is as follows.
1 H NMR (400 MHz, CDCl 3 ) δ 7.82 (1H, d, J = 1.2 Hz), 7.79 (1H, d, J = 15.6 Hz), 7.69-7.67 (2H, m), 7.02 (1H, d, J = 1.2 Hz), 6.95 (1H, d, J = 9.2 Hz), 6.45 (1H, d, J = 15.6 Hz), 4.36 (2H, t, J = 6.8 Hz), 4.22 (2H, t, J = 6.8 Hz), 4.09 (2H, t, J = 6.8 Hz), 4.06 (3H, s), 3.96 (3H, s), 1.90-0.86 (69H, m)
下記化学式（２０）で表される化合物の合成。
実施例５で得られた芳香族化合物４７ｍｇを１５ｍＬのＣＨ2Ｃｌ2に溶解し、そこにＣｕ（ＯＨ）Ｃｌ・ＴＭＥＤＡ２５ｍｇを加え、室温で１５時間攪拌を行った。溶媒を留去した後プレパラティブＴＬＣで精製を行い、目的生成物４３ｍｇを得た。得られた式（２０）に示す芳香族化合物のスペクトルデータは次の通りである。
1H NMR（400MHz, CDCl3）δ 7.86 (2H, d, J=2.0 Hz), 7.83 (2H, d, J=1.2 Hz), 7.77 (2H, d, J=16.0 Hz), 7.75 (2H, d, J=2.0 Hz), 7.00(2H, d, J=1.2 Hz), 6.45(2H, d, J=16.0 Hz), 6.43 (2H, s), 4.25-3.97 (8H, m), 4.03 (6H, s), 4.02 (6H, s), 1.89-0.91 (36H, m); 13C NMR (100MHz, CDCl3) δ 167.23, 164.01, 161.65, 146.60, 145.41, 145.27, 145.25, 144.05, 131.42, 129.45, 125.53, 123.36, 120.98, 117.48, 116.02, 108.48, 106.01, 69.64, 69.18, 56.43, 56.13, 34.30, 34.26, 26.24, 26.12, 16.62, 16.48, 11.30, 11.23
47 mg of the aromatic compound obtained in Example 5 was dissolved in 15 mL of CH 2 Cl 2 , 25 mg of Cu (OH) Cl · TMEDA was added thereto, and the mixture was stirred at room temperature for 15 hours. After distilling off the solvent, purification was performed by preparative TLC to obtain 43 mg of the desired product. The spectrum data of the obtained aromatic compound represented by the formula (20) is as follows.
1 H NMR (400 MHz, CDCl 3 ) δ 7.86 (2H, d, J = 2.0 Hz), 7.83 (2H, d, J = 1.2 Hz), 7.77 (2H, d, J = 16.0 Hz), 7.75 (2H, d, J = 2.0 Hz), 7.00 (2H, d, J = 1.2 Hz), 6.45 (2H, d, J = 16.0 Hz), 6.43 (2H, s), 4.25-3.97 (8H, m), 4.03 ( 6H, s), 4.02 (6H, s), 1.89-0.91 (36H, m); 13 C NMR (100 MHz, CDCl 3 ) δ 167.23, 164.01, 161.65, 146.60, 145.41, 145.27, 145.25, 144.05, 131.42, 129.45 , 125.53, 123.36, 120.98, 117.48, 116.02, 108.48, 106.01, 69.64, 69.18, 56.43, 56.13, 34.30, 34.26, 26.24, 26.12, 16.62, 16.48, 11.30, 11.23
下記化学式（２１）で表される化合物の合成。
実施例５で得られた芳香族化合物に替えて実施例３で得られた芳香族化合物を原料とた以外は上記実施例１７と同様に反応を行い、目的生成物を得た。得られた式（２１）に示す芳香族化合物のスペクトルデータは次の通りである。
1H NMR（400MHz, CDCl3）δ 7.85 (2H, d, J=2.0 Hz), 7.81 (2H, d, J=1.2 Hz), 7.81 (2H, d, J=16.0 Hz), 7.73 (2H, d, J=2.0 Hz), 7.01 (2H, d, J =1.2 Hz), 6.46 (2H, d, J=16.0 Hz), 6.31 (1H, s), 4.06 (6H, s), 4.03 (6H, s), 3.98 (6H, s), 3.83 (6H, s); 13C NMR (100MHz, CDCl3) δ 167.49, 164.23, 161.52, 146.55, 145.52, 145.42, 145.22, 144.08, 131.40, 129.40, 125.48, 123.30, 120.90, 117.05, 116.12, 111.83, 108.12, 105.91, 56.42, 56.09, 51.82, 51.72
A target product was obtained in the same manner as in Example 17 except that the aromatic compound obtained in Example 3 was used as a raw material instead of the aromatic compound obtained in Example 5. The spectrum data of the obtained aromatic compound represented by the formula (21) is as follows.
1 H NMR (400 MHz, CDCl 3 ) δ 7.85 (2H, d, J = 2.0 Hz), 7.81 (2H, d, J = 1.2 Hz), 7.81 (2H, d, J = 16.0 Hz), 7.73 (2H, d, J = 2.0 Hz), 7.01 (2H, d, J = 1.2 Hz), 6.46 (2H, d, J = 16.0 Hz), 6.31 (1H, s), 4.06 (6H, s), 4.03 (6H, s), 3.98 (6H, s), 3.83 (6H, s); 13 C NMR (100 MHz, CDCl 3 ) δ 167.49, 164.23, 161.52, 146.55, 145.52, 145.42, 145.22, 144.08, 131.40, 129.40, 125.48, 123.30 , 120.90, 117.05, 116.12, 111.83, 108.12, 105.91, 56.42, 56.09, 51.82, 51.72
下記化学式（２２）で表される化合物の合成。
実施例５で得られた芳香族化合物に替えて実施例４で得られた芳香族化合物を原料とした以外は上記実施例１７と同様に反応を行い、目的生成物を得た。得られた式（２２）に示す芳香族化合物のスペクトルデータは次の通りである。
1H NMR（400MHz, CDCl3）δ 7.85 (2H, d, J=2.0 Hz), 7.81 (2H, d, J=1.6 Hz), 7.79 (2H, d, J=16.0 Hz), 7.74 (2H, d, J=2.0 Hz), 7.61 (2H, d, J=1.6 Hz), 6.44 (2H, d, J=16.0 Hz), 6.31 (2H, s), 4.43 (4H, q, J=7.2 Hz), 4.29 (4H, q, J=7.2 Hz), 4.05 (6H, s), 4.03 (6H, s), 1.41 (6H, t, J=3.2 Hz), 1.36 (6H, t, J=3.2 Hz); 13C NMR (100MHz, CDCl3) δ 167.10, 163.81, 161.41, 146.50, 145.35, 145.32, 145.23, 144.08, 131.40, 129.48, 125.48, 123.28, 120.98, 117.44, 116.26, 111.88, 108.41, 105.76, 60.85, 60.50, 56.43, 56.10, 14.38, 14.36
The target product was obtained in the same manner as in Example 17 except that the aromatic compound obtained in Example 4 was used instead of the aromatic compound obtained in Example 5. The spectrum data of the obtained aromatic compound represented by the formula (22) is as follows.
1 H NMR (400 MHz, CDCl 3 ) δ 7.85 (2H, d, J = 2.0 Hz), 7.81 (2H, d, J = 1.6 Hz), 7.79 (2H, d, J = 16.0 Hz), 7.74 (2H, d, J = 2.0 Hz), 7.61 (2H, d, J = 1.6 Hz), 6.44 (2H, d, J = 16.0 Hz), 6.31 (2H, s), 4.43 (4H, q, J = 7.2 Hz) , 4.29 (4H, q, J = 7.2 Hz), 4.05 (6H, s), 4.03 (6H, s), 1.41 (6H, t, J = 3.2 Hz), 1.36 (6H, t, J = 3.2 Hz) ; 13 C NMR (100 MHz, CDCl 3 ) δ 167.10, 163.81, 161.41, 146.50, 145.35, 145.32, 145.23, 144.08, 131.40, 129.48, 125.48, 123.28, 120.98, 117.44, 116.26, 111.88, 108.41, 105.76, 60.85, 60.50 , 56.43, 56.10, 14.38, 14.36
下記化学式（２３）で表される化合物の合成。
1H NMR（400MHz, CDCl3）δ 7.93 (2H, d, J=2.0 Hz), 7.82 (2H, d, J=1.6 Hz), 7.81 (2H, d, J=16.0 Hz), 7.61 (2H, d, J=2.0 Hz), 7.03 (2H, d, J=1.6 Hz), 6.47 (2H, d, J=16.0 Hz), 4.03 (6H, s), 3.98 (6H, s), 3.98 (6H, s), 3.83 (6H, s), 2.18 (6H, s); 13C NMR (100MHz, CDCl3) δ 168.22, 167.46, 163.95, 160.24, 151.10, 149.81, 145.37, 144.37, 139.56, 131.63, 130.91, 129.13, 127.17, 124.17, 117.27, 116.17, 113.55, 109.48, 106.21, 56.39, 56.10, 51.94, 51.74, 20.49
Synthesis of a compound represented by the following chemical formula (23).
1 H NMR (400 MHz, CDCl 3 ) δ 7.93 (2H, d, J = 2.0 Hz), 7.82 (2H, d, J = 1.6 Hz), 7.81 (2H, d, J = 16.0 Hz), 7.61 (2H, d, J = 2.0 Hz), 7.03 (2H, d, J = 1.6 Hz), 6.47 (2H, d, J = 16.0 Hz), 4.03 (6H, s), 3.98 (6H, s), 3.98 (6H, s), 3.83 (6H, s), 2.18 (6H, s); 13 C NMR (100 MHz, CDCl 3 ) δ 168.22, 167.46, 163.95, 160.24, 151.10, 149.81, 145.37, 144.37, 139.56, 131.63, 130.91, 129.13 , 127.17, 124.17, 117.27, 116.17, 113.55, 109.48, 106.21, 56.39, 56.10, 51.94, 51.74, 20.49
図１に、実施例３において合成を行った化学式（６）で示す芳香族化合物の紫外線吸収スペクトルを太線で、従来紫外線吸収剤として使用されているフェルラ酸メチルの紫外線吸収スペクトル細線で示す。また、図２には実施例１８において合成を行った化学式（２１）で示す芳香族化合物の紫外線吸収スペクトルを太線で、図１と同じくフェルラ酸メチルの紫外線吸収スペクトルを細線で示す。 In FIG. 1, the ultraviolet absorption spectrum of the aromatic compound represented by the chemical formula (6) synthesized in Example 3 is indicated by a thick line, and the ultraviolet absorption spectrum fine line of methyl ferulate conventionally used as an ultraviolet absorber. FIG. 2 shows the ultraviolet absorption spectrum of the aromatic compound represented by the chemical formula (21) synthesized in Example 18 with a thick line, and the ultraviolet absorption spectrum of methyl ferulate with a thin line as in FIG.
図１，２より、実施例３，１８で得られた化学式（６），（２１）で示す芳香族化合物は全波長でフェルラ酸メチルより高い吸光度を示し、特にフェルラ酸メチルは吸収できない３２０ｎｍ〜４００ｎｍのＵＶ−Ａの紫外線についても高い吸収度を示していることが分かる。 1 and 2, the aromatic compounds represented by the chemical formulas (6) and (21) obtained in Examples 3 and 18 have higher absorbance than methyl ferulate at all wavelengths, and in particular, methyl ferulate cannot absorb 320 nm to It can be seen that the UV-A ultraviolet ray of 400 nm also shows a high absorbance.
また、実施例１，２，４〜１６において合成を行った式（１）で表される芳香族化合物の紫外線吸収スペクトルについても、図１と略同様の結果が得られた。よって、式（１）で表される芳香族化合物は全波長でフェルラ酸メチルより高い吸光度を示すとともに、ＵＶ−Ａの紫外線についても高い吸収度を示していることが分かる。また、実施例１７，１９，２０において合成を行った式（２）で表される芳香族化合物の紫外線吸収スペクトルについても、図２と略同様の結果が得られた。これより、式（１）と同様に、式（２）で表される芳香族化合物が全波長でフェルラ酸メチルより高い吸光度を示すとともに、ＵＶ−Ａの紫外線についても高い吸収度を示していることが分かる。 Moreover, about the ultraviolet absorption spectrum of the aromatic compound represented by the formula (1) synthesized in Examples 1, 2, 4 to 16, the same results as in FIG. 1 were obtained. Therefore, it can be seen that the aromatic compound represented by the formula (1) exhibits higher absorbance than methyl ferulate at all wavelengths and also exhibits higher absorbance for UV-A ultraviolet rays. In addition, the results similar to those in FIG. 2 were obtained for the ultraviolet absorption spectra of the aromatic compounds represented by the formula (2) synthesized in Examples 17, 19, and 20. Thus, as with the formula (1), the aromatic compound represented by the formula (2) exhibits higher absorbance than methyl ferulate at all wavelengths, and also exhibits high absorbance for UV-A ultraviolet rays. I understand that.
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