JP2004099570A - Tetrahydropyranylated polynuclear phenols - Google Patents
Tetrahydropyranylated polynuclear phenols Download PDFInfo
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- JP2004099570A JP2004099570A JP2002267011A JP2002267011A JP2004099570A JP 2004099570 A JP2004099570 A JP 2004099570A JP 2002267011 A JP2002267011 A JP 2002267011A JP 2002267011 A JP2002267011 A JP 2002267011A JP 2004099570 A JP2004099570 A JP 2004099570A
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- tetrahydropyranyl group
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- tetrahydropyranylated
- hydrogen atom
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- 150000002989 phenols Chemical class 0.000 title claims description 14
- 125000001412 tetrahydropyranyl group Chemical group 0.000 claims abstract description 39
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 27
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 abstract description 12
- 238000004090 dissolution Methods 0.000 abstract description 5
- 239000011342 resin composition Substances 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000003504 photosensitizing agent Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 24
- 239000002904 solvent Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- -1 phenol compound Chemical class 0.000 description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000004821 distillation Methods 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000007858 starting material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000013076 target substance Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 235000013824 polyphenols Nutrition 0.000 description 5
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- BXVXPASMKWYBFD-UHFFFAOYSA-N 2-[[2-hydroxy-3-(hydroxymethyl)-5-methylphenyl]methyl]-6-(hydroxymethyl)-4-methylphenol Chemical compound CC1=CC(CO)=C(O)C(CC=2C(=C(CO)C=C(C)C=2)O)=C1 BXVXPASMKWYBFD-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 3
- FNFYXIMJKWENNK-UHFFFAOYSA-N 4-[(2,4-dihydroxyphenyl)methyl]benzene-1,3-diol Chemical compound OC1=CC(O)=CC=C1CC1=CC=C(O)C=C1O FNFYXIMJKWENNK-UHFFFAOYSA-N 0.000 description 3
- WVMWFSJEDURTRX-UHFFFAOYSA-N 4-[(2-hydroxy-5-methylphenyl)methyl]benzene-1,3-diol Chemical compound CC1=CC=C(O)C(CC=2C(=CC(O)=CC=2)O)=C1 WVMWFSJEDURTRX-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 0 Cc(cc1Cc2cc(C)cc(Cc(c(O*)c3)ccc3O*)c2O*)cc(Cc(ccc(O*)c2)c2O*)c1O* Chemical compound Cc(cc1Cc2cc(C)cc(Cc(c(O*)c3)ccc3O*)c2O*)cc(Cc(ccc(O*)c2)c2O*)c1O* 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WXNRYSGJLQFHBR-UHFFFAOYSA-N bis(2,4-dihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O WXNRYSGJLQFHBR-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- OOBDZXQTZWOBBQ-UHFFFAOYSA-N hexaphenol Chemical class C1C2=CC(O)=C(O)C=C2CC2=CC(O)=C(O)C=C2CC2=C1C=C(O)C(O)=C2 OOBDZXQTZWOBBQ-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
Landscapes
- Pyrane Compounds (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
【０００１】
【産業上の利用分野】
本発明は、感光性樹脂組成物における感光剤や溶解抑制剤等として有用である新規なテトラヒドロピラニル化多核フェノール類に関する。
【０００２】
【従来の技術】
従来、フェノール性水酸基を有する２つ以上の芳香核をそれぞれメチレン結合にて結合してなる多核フェノール化合物をエステル化又はエーテル化した化合物は既に幾つか知られている。例えば、ペンタフェノール系化合物の１，２−ナフトキノンジアジド−４又は５−スルホニルエステル化合物（特許文献１参照）、上記とは別異のペンタフェノール系化合物の１，２−ナフトキノンジアジド−４又は５−スルホニルエステル化合物（特許文献２参照）、テトラフェノール系化合物の１，２−ナフトキノンジアジド−４又は５−スルホニルエステル化合物（特許文献３参照）、テトラフェノール系化合物のテトラヒドロピラニル化物やヘキサフェノール系化合物のテトラヒドロピラニル化物（特許文献４参照）等が知られており、これらの化合物は、感光性樹脂組成物における感光剤や溶解抑制剤等として有用であることも知られている。
【０００３】
【特許文献１】特開平９−１１０７６２号公報第２〜３頁
【特許文献２】特開平９−２９１０５６号公報第２〜３頁
【特許文献３】特開平８−２４５４６１号公報第３頁
【特許文献４】特開平７−２７１０３７号公報第４７〜４８頁
【０００４】
【発明が解決しようとする課題】
近時、感光性樹脂組成物における感光剤や溶解抑制剤等に要求される性能は益々高度化、多様化してきており、本発明者らは、このような事情の下、鋭意研究した結果、上記用途に用いることができる新規なテトラヒドロピラニル化多核フェノール類を見出して、本発明を完成した。
【０００５】
【課題を解決するための手段】
本発明によれば、一般式（Ｉ）
【０００６】
【化１０】
（式中、Ｒ１ は水素原子又はテトラヒドロピラニル基を示し、
（ａ）Ｒ３ 、Ｒ８ 、Ｒ５ 及びＲ６ が水素原子であるとき、Ｒ２ 、Ｒ４ 及びＲ７ はいずれもそれぞれ独立して−ＯＲ１ 基であり（但し、Ｒ１ は上記と同じであり、４つの−ＯＲ１ 基のうち、少なくとも１つはテトラヒドロピラニル基である。）、
（ｂ）Ｒ３ 及びＲ８ がいずれも独立して一般式（ＩＩ）
【０００８】
【化１１】
（式中、Ｒ１ は水素原子又はテトラヒドロピラニル基を示す。）
で表される基であり、Ｒ２ が−ＯＲ１ 基であるとき（但し、Ｒ１ は上記と同じであり、４つの−ＯＲ１ 基のうち、少なくとも１つはテトラヒドロピラニル基である。）、Ｒ４ 及びＲ７ は水素原子であり、Ｒ５ 及びＲ６ はメチル基であり、
（ｃ）Ｒ３ 及びＲ８ がそれぞれいずれも独立して一般式（ＩＩＩ）
【００１０】
【化１２】
（式中、Ｒ１ はそれぞれ独立して水素原子又はテトラヒドロピラニル基を示す。）
で表される基であり、Ｒ２ が−ＯＲ１ 基であるとき（但し、Ｒ１ は上記と同じであり、６つの−ＯＲ１ 基のうち、少なくとも１つはテトラヒドロピラニル基である。）、Ｒ４ 及びＲ７ は水素原子であり、Ｒ５ 及びＲ６ はメチル基であり、
（ｄ）Ｒ３ が一般式（ＩＶ）
【００１２】
【化１３】
（式中、Ｒ１ は水素原子又はテトラヒドロピラニル基を示し、ベンゼン環上の−ＯＲ１ 基の結合位置はメチレン基の結合位置に対してオルト位又はパラ位である。）
で表される基であり、Ｒ８ が一般式（Ｖ）
【００１４】
【化１４】
（式中、Ｒ１ はそれぞれ独立して水素原子又はテトラヒドロピラニル基を示し、末端のベンゼン環上の−ＯＲ１ 基の結合位置はメチレン基の結合位置に対してオルト位又はパラ位である。）
で表される基であり、Ｒ４ が−ＯＲ１ 基であるとき（但し、Ｒ１ は上記と同じであり、５つの−ＯＲ１ 基のうち、少なくとも１つはテトラヒドロピラニル基である。）、Ｒ７ は水素原子であり、Ｒ２ 、Ｒ５ 及びＲ６ はメチル基である。）
で表されるテトラヒドロピラニル化多核フェノール類が提供される。
【００１６】
【発明の実施の形態】
即ち、本発明によれば、
（ａ）一般式（ＶＩ）
【００１７】
【化１５】
（式中、Ｒはそれぞれ独立して水素原子又はテトラヒドロピラニル基を示し、分子の両末端の−ＯＲ基の結合位置はメチレン基の結合位置に対してオルト位又はパラ位である（但し、５つのＲのうち、少なくとも１つはテトラヒドロピラニル基である。）。）
で表されるテトラヒドロピラニル化多核フェノール類、
（ｂ）一般式（ＶＩＩ）
【００１９】
【化１６】
（式中、Ｒはそれぞれ独立して水素原子又はテトラヒドロピラニル基を示す（但し、４つのＲのうち、少なくとも１つはテトラヒドロピラニル基である。）。）で表されるテトラヒドロピラニル化多核フェノール類、
（ｃ）一般式（ＶＩＩＩ）
【００２１】
【化１７】
（式中、Ｒはそれぞれ独立して水素原子又はテトラヒドロピラニル基を示す（但し、６つのＲのうち、少なくとも１つはテトラヒドロピラニル基である。）。）で表されるテトラヒドロピラニル化多核フェノール類、又は
（ｄ）一般式（ＩＸ）
【００２３】
【化１８】
（式中、Ｒはそれぞれ独立して水素原子又はテトラヒドロピラニル基を示し、分子の両末端のベンゼン環上の−ＯＲ基の結合位置はメチレン基の結合位置に対してオルト位又はパラ位である（但し、５つのＲのうち、少なくとも１つはテトラヒドロピラニル基である。）。）
で表されるテトラヒドロピラニル化多核フェノール類が提供される。
【００２５】
本発明によるこのようなテトラヒドロピラニル化多核フェノール類は、原料として、対応する多核フェノールを用い、これに酸触媒の存在下に３，４−ジヒドロ−２Ｈ−ピランを反応させることによって得ることができる。
【００２６】
即ち、前記一般式（ＶＩ）で表わされるテトラヒドロピラニル化多核フェノール類を得るには、原料として、次式（１）
【００２７】
【化１９】
で示される多核フェノールが用いられ、前記一般式（ＶＩＩ） で表わされるテトラヒドロピラニル化多核フェノール類を得るには、原料として、次式（２）
【００２９】
【化２０】
で示される多核フェノールが用いられ、前記一般式（ＶＩＩＩ）で表わされるテトラヒドロピラニル化多核フェノール類を得るには、原料として、次式（３）
【００３１】
【化２１】
で示される多核フェノールが用いられ、そして、前記一般式（ＩＸ）で表わされるテトラヒドロピラニル化多核フェノール類を得るには、原料として、次式（４）
【００３３】
【化２２】
（式中、分子の両末端のベンゼン環上の水酸基の結合位置はメチレン基の結合位置に対してオルト位又はパラ位である。）
で示される多核フェノールが用いられる。
【００３５】
原料多核フェノールとの反応において、３，４−ジヒドロ−２Ｈ−ピランは、原料多核フェノールの水酸基当量に対して、通常、２〜３０モル倍、好ましくは、２〜１０モル倍の範囲で用いられる。また、酸触媒としては、塩酸、硫酸等の無機酸、酢酸、プロピオン酸、ｐ−トルエンスルホン酸等の有機酸、ｐ−トルエンスルホン酸ピリジン塩等の有機酸塩が用いられるが、好ましくは、ｐ−トルエンスルホン酸やそのピリジン塩が用いられる。しかし、これらに限定されるものではない。このような酸触媒は、原料多核フェノールに対して、通常、０．１〜１０重量％、好ましくは、０．５〜５重量％の範囲で用いられる。
【００３６】
原料多核フェノールと３，４−ジヒドロ−２Ｈ−ピランとの反応は、好ましくは、反応溶媒の存在下、通常、大気圧下に、０〜４０℃、好ましくは、２０〜３０℃の範囲の温度で行われる。上記反応溶媒としては、例えば、メチルイソブチルケトン等のケトン溶媒、テトラヒドロフラン等のエーテル溶媒 酢酸エチル等のエステル溶媒が好ましく用いられるが、なかでも、テトラヒドロフランが好ましく用いられる。このような溶媒は、通常、原料多核フェノールに対して、２〜１０重量倍、好ましくは、２〜５重量倍の範囲で用いられる。このような条件下において、反応は、通常、５〜２００時間程度で完結する。
【００３７】
反応終了後、目的とする反応生成物を精製するには、例えば、得られた反応混合物にアルカリ水溶液を加えて中和し、水層を分液等により除去して、目的物を含む油層を得、これを必要に応じて水洗した後、減圧蒸留等を行って溶媒を除去すれば、目的物を固形物として得ることができる。
【００３８】
このように、本発明によるテトラヒドロピラニル化多核フェノール類は、原料多核フェノール類に３，４−ジヒドロ−２Ｈ−ピランを反応させて、そのフェノール性水酸基の水素原子の少なくとも１つをテトラヒドロピラニル基で置換することによって得ることができる。従って、本発明によるテトラヒドロピラニル化多核フェノール類は、通常、テトラヒドロピラニル基による置換数の異なる複数の多置換体の混合物として得られるが、そのような混合物は、通常、そのままで、例えば、感光剤レジスト原料等として好適に用いられる。
【００３９】
本発明によれば、前記一般式（ＶＩ）又は一般式（ＶＩＩ） で表わされるテトラヒドロピラニル化多核フェノール類はそれぞれ、好ましくは、主として、３置換体と４置換体との混合物からなり、一般式（ＶＩＩＩ）で表わされるテトラヒドロピラニル化多核フェノール類は、好ましくは、主として、５置換体と６置換体との混合物からなり、前記一般式（ＩＸ）で表わされるテトラヒドロピラニル化多核フェノール類は、好ましくは、主として、４置換体と５置換体との混合物からなる。
【００４０】
【実施例】
以下に実施例を挙げて本発明を説明するが、本発明はこれら実施例により何ら限定されるものではない。
【００４１】
参考例１（原料多核フェノール（１）の合成）
１Ｌ容量のオートクレーブに２，２’，４，４’−テトラヒドロキシベンゾフェノン５０ｇ（０．２５３モル）、ジオキサン１５０ｇ及び銅クロム触媒１５ｇを仕込み、攪拌下に温度１６０℃、水素圧９０Ｋｇ／ｃｍ２ において、約１時間、水素化反応を行った。
【００４２】
反応終了後、反応混合物から触媒を濾別し、得られた反応混合物を減圧蒸留して、溶媒を一部留去し濃縮した。得られた残留液にメチルイソブチルケトンと水を加え、水洗した後、水層を分液して、目的物を含む油層を得た。この油層から晶析、濾過により、目的物である２，２’−メチレンビス（５−ヒドロキシフェノール）２８．３ｇを橙色結晶として得た。高速液体クロマトグラフィーによる純度は９９．６％、原料２，２’，４，４’−テトラヒドロキシベンゾフェノンに対する収率は６０％であった。
【００４３】
プロトンＮＭＲ分析（ジメチルスルホキシド溶媒、４００ＭＨｚ、δ（ｐｐｍ））：
【００４４】
【化２３】
【表１】
実施例１（テトラヒドロピラニル化多核フェノール（ＶＩ）の合成）
１Ｌ容量の４つ口フラスコに上記参考例１で得られた２，２’−メチレンビス（５−ヒドロキシフェノール）２３．２ｇ（０．１モル）、ｐ−トルエンスルホン酸ピリジン塩０．１２ｇ及びテトラヒドロフラン８０ｇを仕込み、室温下、攪拌しながら、３，４−ジヒドロ−２−Ｈ−ピラン１６８ｇ（２．０モル）を２時間かけて滴下した。滴下終了後、上記と同じ温度で更に２日間攪拌下に反応を行った。
【００４７】
反応終了後、得られた反応混合物に２５％テトラメチルアンモニウムヒドロキシド水溶液０．２ｇと水１５８ｇを加えて攪拌、中和し、その後、水層を分液除去して、目的物を含む油層を得、この油層を水１６０ｇで水洗した。この水洗を３回繰り返した後、油層から減圧蒸留にて溶媒を留去して、目的物として蒸留残渣５８．２ｇを 色固体として得た。原料２，２’−メチレンビス（５−ヒドロキシフェノール）に対する収率は１０２％（溶媒残渣を含む。）、高速液体クロマトグラフィー分析による純度８６．１％、置換体の組成比は３置換体２．９％、４置換体９７．１％であった。
【００４８】
プロトンＮＭＲ分析（ジメチルスルホキシド溶媒、４００ＭＨｚ、化学シフトδ（ｐｐｍ））：
【００４９】
【化２４】
【表２】
参考例２（原料多核フェノール（２）の合成）
１Ｌ容量の四つ口フフラスコに２，２’−メチレンビス（４−メチル−６−ヒドロキシメチルフェノール）５７．６ｇ、メチルイソブチルケトン１７２．８ｇ、ｐ−クレゾール２１６ｇ及びｐ−トルエンスルホン酸１．７ｇを仕込み、温度６０℃で攪拌下に１８時間反応を行った。反応終了後、得られた反応混合物に１６％水酸化ナトリウム水溶液を加えて中和した後、水層を分液除去し、目的物を含む油層を得、この油層を水洗した後、減圧蒸留にて濃縮し、残留液から晶析、濾過して、目的物である２，２’−メチレンビス（（６−（５−メチル−２−ヒドロキシフェニル）メチル）−４−メチルフェノール）７３．９ｇを淡黄色固体として得た。原料２，２’−メチレンビス（４−メチル−６−ヒドロキシメチルフェノール）に対する収率は８０％、高速液体クロマトグラフィー分析による純度は７３．１％であった。
【００５２】
プロトンＮＭＲ分析（ジメチルスルホキシド溶媒、４００ＭＨｚ、化学シフトδ（ｐｐｍ））：
【００５３】
【化２５】
【表３】
実施例２（テトラヒドロピラニル化多核フェノール（ＶＩＩ） の合成）
１Ｌ容量の四つ口フラスコに上記参考例２で得られた２，２’−メチレンビス（（６−（５−メチル−２−ヒドロキシフェニル）メチル）−４−メチルフェノール）４６．８ｇ（０．１モル）、ｐ−トルエンスルホン酸ピリジン塩２．３ｇ及びテトラヒドロフラン９５ｇを仕込み、室温下、攪拌しながら、３，４−ジヒドロ−２−Ｈ−ピラン６７．３ｇ（０．８モル）を１時間かけて滴下した。滴下終了後、上記と同じ温度で更に７日間攪拌下に反応を行い、この間に３，４−ジヒドロ−２−Ｈ−ピラン２０１．６ｇ（２．４モル）を更に加えた。
【００５６】
反応終了後、得られた反応混合物に２５％テトラメチルアンモニウムヒドロキシド水溶液０．９ｇと水１００ｇを加えて攪拌、中和し、その後、水層を分液除去し、目的物を含む油層を得、これを水１６０ｇで水洗した。この水洗を３回繰り返した後、油層から減圧蒸留にて溶媒を留去して、蒸留残渣として目的物である置換ポリフェノール化合物８５．６ｇを黄色固体として得た。原料２，２’−メチレンビス（（６−（５−メチル−２−ヒドロキシフェニル）メチル）−４−メチルフェノール）に対する収率は１１９％（溶媒残渣を含む。）、高速液体クロマトグラフィー分析による純度は７０．１％、置換体の組成比は３置換体４２．２％、４置換体５７．８％であった。
【００５７】
プロトンＮＭＲ分析（ジメチルスルホキシド溶媒、４００ＭＨｚ、化学シフトδ（ｐｐｍ））：
（３置換体の一例）
【００５８】
【化２６】
【表４】
参考例３（原料多核フェノール（３）の合成）
１Ｌ容量の四つ口フフラスコに２，２’−メチレンビス（４−メチル−６−ヒドロキシメチルフェノール）７２ｇ、レゾルシン１９２．７ｇ、水５７８ｇ及び濃塩酸５７．８ｇを仕込み、温度３０℃で攪拌しながら、２時間反応を行った。反応終了後、得られた反応混合物に１６％水酸化ナトリウム水溶液を加えて中和し、メチルイソブチルケトンを加えた後、水層を分液除去して、目的物を含む油層を得、これを水洗した後、油層を減圧蒸留し、残留液から晶出、濾過にて目的物である２，２’−メチレンビス（６−（２，４−ジヒドロキシフェニル）メチル）４−メチルフェノール）５１．８ｇを淡黄色固体として得た。原料２，２’−メチレンビス（４−メチル−６−ヒドロキシメチルフェノール）に対する収率は４４％、高速液体クロマトグラフィー分析によるは純度８２．７％であった。
【００６１】
プロトンＮＭＲ分析（ジメチルスルホキシド溶媒、４００ＭＨｚ、化学シフトδ（ｐｐｍ））：
【００６２】
【化２７】
【表５】
実施例３（テトラヒドロピラニル化多核フェノール（ＶＩＩＩ）の合成）
１Ｌ容量の四つ口フラスコに上記参考例３で得られた２，２’−メチレンビス（６−（２，４−ジヒドロキシフェニル）メチル）４−メチルフェノール）１８．９ｇ（０．０４モル）及び３，４−ジヒドロ−２−Ｈ−ピラン６０．５ｇ（０．７２モル）を仕込み、氷冷下、攪拌しながら、ｐ−トルエンスルホン酸ピリジン塩１．０ｇを添加した。添加終了後、上記と同じ温度で更に３日間攪拌下に反応を行い、この間に３，４−ジヒドロ−２−Ｈ−ピラン８０．６ｇ（０．９６モル）を更に加えた。
【００６５】
反応終了後、得られた反応混合物に２０％テトラメチルアンモニウムヒドロキシド水溶液１．８ｇと水５０ｇを加えて攪拌、中和し、その後、水層を分液除去して、目的物を含む油層を得、これを水１６０ｇで水洗した。この水洗を３回繰り返した後、油層から減圧蒸留にて溶媒を留去して、蒸留残渣として、目的物である置換ポリフェノール化合物４４．９ｇを茶色固体として得た。原料２，２’−メチレンビス（６−（２，４−ジヒドロキシフェニル）メチル）４−メチルフェノール）に対する収率は１１５％（溶媒残渣を含む。）、高速液体クロマトグラフィー分析による純度は７７．９％、置換体の組成比は５置換体５０．４％、６置換体４９．６％であった。
【００６６】
プロトンＮＭＲ分析（ジメチルスルホキシド溶媒、４００ＭＨｚ、化学シフトδ（ｐｐｍ））：
（５置換体の一例）
【００６７】
【化２８】
【表６】
参考例４（原料多核フェノール（４）の合成）
１Ｌ容量の四つ口フラスコに２，６−ジ（４−ヒドロキシ−２，５−ジメチルフェニル）メチル−４−メチルフェノール８７．２ｇ、フェノール１７４．５ｇ、メチルイソブチルケトン４３．６ｇ及びｐ−トルエンスルホン２．７ｇを仕込み、温度３０℃で攪拌しながら、５時間反応を行った。反応終了後、得られた反応混合物に１６％水酸化ナトリウム水溶液を加えて中和した後、水層を分液除去して、目的物を含む油層を得、これを水洗した後、油層を減圧蒸留して、残液から晶出、濾過にて目的物である多核フェノール化合物４８．５ｇを白色固体として得た。原料２，６−ジ（４−ヒドロキシ−２，５−ジメチルフェニル）メチル−４−メチルフェノールに対する収率は４１％、高速液体クロマトグラフィー分析による純度は８２．７％であった。
【００７０】
プロトンＮＭＲ分析（ジメチルスルホキシド溶媒、４００ＭＨｚ、化学シフトδ（ｐｐｍ））：
【００７１】
【化２９】
（式中、分子の両末端のベンゼン環上の水酸基の結合位置はメチレン基の結合位置に対してオルト位又はパラ位である。）
【００７３】
【表７】
実施例４（テトラヒドロピラニル化多核フェノール（ＩＸ）の合成）
１Ｌ容量の四つ口フラスコに上記参考例４で得られた多核フェノール４１．２ｇ（０．０７モル）、ｐ−トルエンスルホン酸ピリジン塩３．６ｇ及びテトラヒドロフラン１０８ｇを仕込み、室温で攪拌しながら、３，４−ジヒドロ−２−Ｈ−ピラン１１８ｇ（１．４モル）を２時間かけて滴下した。滴下終了後、上記と同じ温度で更に３日間攪拌下に反応を行い、この間に３，４−ジヒドロ−２−Ｈ−ピラン１１８ｇ（１．４モル）を更に加えた。
【００７５】
反応終了後、得られた反応混合物に２５％テトラメチルアンモニウムヒドロキシド水溶液０．５ｇと水２００ｇを加えて攪拌、中和し、その後、水層を分液除去して、目的物を含む油層を得、これを水１６０ｇで水洗した。この水洗を３回繰り返した後、油層から減圧蒸留にて溶媒を留去して、蒸留残渣として、目的物である置換ポリフェノール化合物８２．６ｇを茶色固体として得た。原料多核フェノール化合物に対する収率は１１７％（溶媒残渣を含む。）、高速液体クロマトグラフィー分析による純度は６８．１％、置換体の組成比は３置換体２．９％、４置換体２５．７％、５置換体７１．４％であった。
【００７６】
プロトンＮＭＲ分析（ジメチルスルホキシド溶媒、４００ＭＨｚ、化学シフトδ（ｐｐｍ））：
（４置換体の一例）
【００７７】
【化３０】
【表８】
本発明によるテトラヒドロピラニル化多核フェノール類は、好ましい態様によれば、分子内に２つ以上のテトラヒドロピラニル基を有し、感光性樹脂組成物における感光剤や溶解抑制剤等として有用である。[0001]
[Industrial applications]
The present invention relates to novel tetrahydropyranylated polynuclear phenols useful as a photosensitizer, a dissolution inhibitor and the like in a photosensitive resin composition.
[0002]
[Prior art]
BACKGROUND ART Heretofore, some compounds obtained by esterifying or etherifying a polynuclear phenol compound obtained by bonding two or more aromatic nuclei each having a phenolic hydroxyl group with a methylene bond are already known. For example, a 1,2-naphthoquinonediazide-4 or 5-sulfonylester compound of a pentaphenol-based compound (see Patent Document 1), and a 1,2-naphthoquinonediazide-4 or 5- of a pentaphenol-based compound different from the above. Sulfonyl ester compounds (see Patent Document 2), 1,2-naphthoquinonediazide-4 or 5-sulfonyl ester compounds of tetraphenol compounds (see Patent Document 3), tetrahydropyranylated tetraphenol compounds, and hexaphenol compounds And the like (see Patent Document 4), and it is also known that these compounds are useful as a photosensitive agent, a dissolution inhibitor and the like in a photosensitive resin composition.
[0003]
[Patent Document 1] Japanese Patent Application Laid-Open No. Hei 9-110762, page 2 to 3 [Patent Document 2] Japanese Patent Application Laid-Open No. 9-291506, page 2 to 3 [Patent Document 3] Japanese Patent Application Laid-Open No. 8-245461, page 3 [ [Patent Document 4] JP-A-7-271037, pp. 47-48
[Problems to be solved by the invention]
In recent years, the performance required for a photosensitive agent, a dissolution inhibitor, and the like in a photosensitive resin composition has been increasingly sophisticated and diversified. The present invention has been completed by finding novel tetrahydropyranylated polynuclear phenols that can be used in the above applications.
[0005]
[Means for Solving the Problems]
According to the present invention, general formula (I)
[0006]
Embedded image
(Wherein, R 1 represents a hydrogen atom or a tetrahydropyranyl group,
(A) When R 3 , R 8 , R 5 and R 6 are hydrogen atoms, R 2 , R 4 and R 7 are each independently —OR 1 groups (provided that R 1 is as defined above) The same, at least one of the four —OR 1 groups is a tetrahydropyranyl group),
(B) R 3 and R 8 are each independently of the general formula (II)
[0008]
Embedded image
(In the formula, R 1 represents a hydrogen atom or a tetrahydropyranyl group.)
Wherein R 2 is a —OR 1 group (provided that R 1 is the same as described above, and at least one of the four —OR 1 groups is a tetrahydropyranyl group. ), R 4 and R 7 are hydrogen atoms, R 5 and R 6 are methyl groups,
(C) R 3 and R 8 are each independently a general formula (III)
[0010]
Embedded image
(In the formula, R 1 each independently represents a hydrogen atom or a tetrahydropyranyl group.)
Wherein R 2 is a —OR 1 group (provided that R 1 is the same as described above, and at least one of the six —OR 1 groups is a tetrahydropyranyl group. ), R 4 and R 7 are hydrogen atoms, R 5 and R 6 are methyl groups,
(D) R 3 is a group represented by the general formula (IV)
[0012]
Embedded image
(In the formula, R 1 represents a hydrogen atom or a tetrahydropyranyl group, and the bonding position of the —OR 1 group on the benzene ring is ortho or para with respect to the bonding position of the methylene group.)
Wherein R 8 is a group represented by the general formula (V)
[0014]
Embedded image
(Wherein, R 1 each independently represents a hydrogen atom or a tetrahydropyranyl group, and the bonding position of the —OR 1 group on the terminal benzene ring is ortho or para to the bonding position of the methylene group. .)
Wherein R 4 is a —OR 1 group (provided that R 1 is the same as described above, and at least one of the five —OR 1 groups is a tetrahydropyranyl group. ) And R 7 are hydrogen atoms, and R 2 , R 5 and R 6 are methyl groups. )
And a tetrahydropyranylated polynuclear phenol represented by the formula:
[0016]
BEST MODE FOR CARRYING OUT THE INVENTION
That is, according to the present invention,
(A) General formula (VI)
[0017]
Embedded image
(Wherein, R independently represents a hydrogen atom or a tetrahydropyranyl group, and the bonding positions of the -OR groups at both ends of the molecule are ortho or para to the bonding position of the methylene group (provided that At least one of the five Rs is a tetrahydropyranyl group.))
A tetrahydropyranylated polynuclear phenol represented by
(B) General formula (VII)
[0019]
Embedded image
(In the formula, each R independently represents a hydrogen atom or a tetrahydropyranyl group (provided that at least one of the four Rs is a tetrahydropyranyl group.)) Polynuclear phenols,
(C) General formula (VIII)
[0021]
Embedded image
(In the formula, each R independently represents a hydrogen atom or a tetrahydropyranyl group (provided that at least one of the six Rs is a tetrahydropyranyl group.)) Polynuclear phenols, or (d) general formula (IX)
[0023]
Embedded image
(Wherein R independently represents a hydrogen atom or a tetrahydropyranyl group, and the bonding position of the -OR group on the benzene ring at both ends of the molecule is ortho or para with respect to the bonding position of the methylene group. (However, at least one of the five Rs is a tetrahydropyranyl group.))
And a tetrahydropyranylated polynuclear phenol represented by the formula:
[0025]
Such tetrahydropyranylated polynuclear phenols according to the present invention can be obtained by using the corresponding polynuclear phenol as a raw material and reacting it with 3,4-dihydro-2H-pyran in the presence of an acid catalyst. it can.
[0026]
That is, in order to obtain the tetrahydropyranylated polynuclear phenol represented by the general formula (VI), as a raw material, the following formula (1)
[0027]
Embedded image
In order to obtain a tetrahydropyranylated polynuclear phenol represented by the above general formula (VII), a polynuclear phenol represented by the following formula (2) is used as a raw material.
[0029]
Embedded image
In order to obtain the tetrahydropyranylated polynuclear phenol represented by the general formula (VIII), a polynuclear phenol represented by the following formula (3) is used as a raw material.
[0031]
Embedded image
Is used. In order to obtain the tetrahydropyranylated polynuclear phenol represented by the general formula (IX), the following formula (4) is used as a raw material.
[0033]
Embedded image
(In the formula, the bonding position of the hydroxyl group on the benzene ring at both ends of the molecule is at the ortho position or the para position with respect to the bonding position of the methylene group.)
Is used.
[0035]
In the reaction with the starting polynuclear phenol, 3,4-dihydro-2H-pyran is used in an amount of usually 2 to 30 mol times, preferably 2 to 10 mol times, relative to the hydroxyl equivalent of the starting polynuclear phenol. . Further, as the acid catalyst, inorganic acids such as hydrochloric acid and sulfuric acid, acetic acid, propionic acid, organic acids such as p-toluenesulfonic acid, and organic acid salts such as p-toluenesulfonic acid pyridine salt are preferably used. p-Toluenesulfonic acid and its pyridine salt are used. However, it is not limited to these. Such an acid catalyst is used in an amount of usually 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the starting polynuclear phenol.
[0036]
The reaction between the starting polynuclear phenol and 3,4-dihydro-2H-pyran is preferably carried out in the presence of a reaction solvent, usually at atmospheric pressure, at a temperature of 0 to 40 ° C, preferably 20 to 30 ° C. Done in As the reaction solvent, for example, a ketone solvent such as methyl isobutyl ketone or the like, an ether solvent such as tetrahydrofuran or the like, an ester solvent such as ethyl acetate or the like is preferably used, and among them, tetrahydrofuran is preferably used. Such a solvent is usually used in a range of 2 to 10 times by weight, preferably 2 to 5 times by weight based on the starting polynuclear phenol. Under such conditions, the reaction is usually completed in about 5 to 200 hours.
[0037]
After completion of the reaction, in order to purify the target reaction product, for example, an alkaline aqueous solution is added to the obtained reaction mixture to neutralize it, the aqueous layer is removed by liquid separation, etc., and the oil layer containing the target product is removed. The desired product can be obtained as a solid by washing it with water as required and then removing the solvent by distillation under reduced pressure or the like.
[0038]
As described above, the tetrahydropyranylated polynuclear phenols according to the present invention are obtained by reacting a starting polynuclear phenol with 3,4-dihydro-2H-pyran to convert at least one hydrogen atom of the phenolic hydroxyl group to tetrahydropyranyl. Can be obtained by substitution with a group. Accordingly, the tetrahydropyranylated polynuclear phenols according to the present invention are usually obtained as a mixture of a plurality of polysubstituted compounds having different numbers of substitutions by tetrahydropyranyl groups, and such a mixture is usually used as such, for example, It is suitably used as a material for a photosensitive resist.
[0039]
According to the present invention, each of the tetrahydropyranylated polynuclear phenols represented by the general formula (VI) or (VII) preferably mainly comprises a mixture of a tri-substituted product and a tetra-substituted product. The tetrahydropyranylated polynuclear phenols represented by the formula (VIII) preferably consist mainly of a mixture of penta-substituted and hexa-substituted phenols, and are represented by the general formula (IX). Preferably consists mainly of a mixture of 4- and 5-substituted products.
[0040]
【Example】
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
[0041]
Reference Example 1 (Synthesis of raw material polynuclear phenol (1))
Autoclave 1L capacity 2,2 ', 4,4'-tetra hydroxybenzophenone 50 g (0.253 mol) were charged in dioxane 150g, and a copper chromium catalyst 15 g, temperature 160 ° C. with stirring, at a hydrogen pressure of 90 Kg / cm 2 The hydrogenation reaction was carried out for about 1 hour.
[0042]
After completion of the reaction, the catalyst was separated by filtration from the reaction mixture, and the obtained reaction mixture was distilled under reduced pressure to partially remove the solvent and concentrated. Methyl isobutyl ketone and water were added to the obtained residual liquid, and after washing with water, the aqueous layer was separated to obtain an oil layer containing the desired product. By crystallization and filtration from the oil layer, 28.3 g of 2,2′-methylenebis (5-hydroxyphenol), which was the target substance, was obtained as orange crystals. The purity by high performance liquid chromatography was 99.6%, and the yield based on the starting material 2,2 ′, 4,4′-tetrahydroxybenzophenone was 60%.
[0043]
Proton NMR analysis (dimethyl sulfoxide solvent, 400 MHz, δ (ppm)):
[0044]
Embedded image
[Table 1]
Example 1 (Synthesis of tetrahydropyranylated polynuclear phenol (VI))
In a 1 L four-necked flask, 23.2 g (0.1 mol) of 2,2′-methylenebis (5-hydroxyphenol) obtained in Reference Example 1, 0.12 g of p-toluenesulfonic acid pyridine salt and tetrahydrofuran After charging 80 g, 168 g (2.0 mol) of 3,4-dihydro-2-H-pyran was added dropwise over 2 hours while stirring at room temperature. After the completion of the dropwise addition, the reaction was carried out at the same temperature as above for 2 days with stirring.
[0047]
After completion of the reaction, 0.2 g of a 25% aqueous solution of tetramethylammonium hydroxide and 158 g of water were added to the obtained reaction mixture, and the mixture was stirred and neutralized. Thereafter, the aqueous layer was separated and removed to obtain an oil layer containing the target substance. This oil layer was washed with 160 g of water. After repeating this water washing three times, the solvent was distilled off from the oil layer by distillation under reduced pressure, and 58.2 g of a distillation residue was obtained as the target substance Obtained as a colored solid. The yield based on the starting material 2,2'-methylenebis (5-hydroxyphenol) is 102% (including the solvent residue), the purity is 86.1% by high performance liquid chromatography analysis, and the composition ratio of the substituted product is 2. It was 97.1% and 97.1% of 4-substituted products.
[0048]
Proton NMR analysis (dimethyl sulfoxide solvent, 400 MHz, chemical shift δ (ppm)):
[0049]
Embedded image
[Table 2]
Reference Example 2 (Synthesis of raw material polynuclear phenol (2))
57.6 g of 2,2'-methylenebis (4-methyl-6-hydroxymethylphenol), 172.8 g of methyl isobutyl ketone, 216 g of p-cresol and 1.7 g of p-toluenesulfonic acid were placed in a 1 L four-necked flask. The mixture was charged and reacted at a temperature of 60 ° C. with stirring for 18 hours. After completion of the reaction, the obtained reaction mixture was neutralized by adding a 16% aqueous solution of sodium hydroxide, and then the aqueous layer was separated and removed to obtain an oil layer containing the desired product. The oil layer was washed with water and then distilled under reduced pressure. Then, the residue was crystallized from the residue and filtered to obtain 73.9 g of 2,2′-methylenebis ((6- (5-methyl-2-hydroxyphenyl) methyl) -4-methylphenol) as a target substance. Obtained as a pale yellow solid. The yield based on the starting material 2,2′-methylenebis (4-methyl-6-hydroxymethylphenol) was 80%, and the purity by high performance liquid chromatography analysis was 73.1%.
[0052]
Proton NMR analysis (dimethyl sulfoxide solvent, 400 MHz, chemical shift δ (ppm)):
[0053]
Embedded image
[Table 3]
Example 2 (Synthesis of tetrahydropyranylated polynuclear phenol (VII))
In a 1 L four-necked flask, 46.8 g of the 2,2′-methylenebis ((6- (5-methyl-2-hydroxyphenyl) methyl) -4-methylphenol) obtained in Reference Example 2 (0. 1 mol), 2.3 g of p-toluenesulfonic acid pyridine salt and 95 g of tetrahydrofuran, and 67.3 g (0.8 mol) of 3,4-dihydro-2-H-pyran for 1 hour with stirring at room temperature. The solution was dropped. After the completion of the dropwise addition, the reaction was further carried out with stirring at the same temperature as above for 7 days, during which time 201.6 g (2.4 mol) of 3,4-dihydro-2-H-pyran was further added.
[0056]
After completion of the reaction, 0.9 g of a 25% aqueous solution of tetramethylammonium hydroxide and 100 g of water were added to the obtained reaction mixture, and the mixture was stirred and neutralized. Thereafter, the aqueous layer was separated and removed to obtain an oil layer containing the desired product. This was washed with 160 g of water. After repeating this water washing three times, the solvent was distilled off from the oil layer by distillation under reduced pressure to obtain 85.6 g of the objective substituted polyphenol compound as a distillation residue as a yellow solid. The yield based on the starting material 2,2'-methylenebis ((6- (5-methyl-2-hydroxyphenyl) methyl) -4-methylphenol) was 119% (including the solvent residue), and the purity by high performance liquid chromatography analysis. Was 70.1%, and the composition ratio of the substituted product was 42.2% for the 3-substituted product and 57.8% for the 4-substituted product.
[0057]
Proton NMR analysis (dimethyl sulfoxide solvent, 400 MHz, chemical shift δ (ppm)):
(Example of tri-substituted product)
[0058]
Embedded image
[Table 4]
Reference Example 3 (Synthesis of raw material polynuclear phenol (3))
A 1 L four-necked flask was charged with 72 g of 2,2′-methylenebis (4-methyl-6-hydroxymethylphenol), 192.7 g of resorcin, 578 g of water and 57.8 g of concentrated hydrochloric acid, and stirred at a temperature of 30 ° C. The reaction was performed for 2 hours. After completion of the reaction, the obtained reaction mixture was neutralized by adding a 16% aqueous sodium hydroxide solution, and methyl isobutyl ketone was added. Then, the aqueous layer was separated and removed to obtain an oil layer containing the desired product. After washing with water, the oil layer was distilled under reduced pressure, crystallized from the residual liquid, and filtered to obtain 51.8 g of 2,2′-methylenebis (6- (2,4-dihydroxyphenyl) methyl) 4-methylphenol, which was the target substance. Was obtained as a pale yellow solid. The yield based on the starting material 2,2'-methylenebis (4-methyl-6-hydroxymethylphenol) was 44%, and the purity by high performance liquid chromatography was 82.7%.
[0061]
Proton NMR analysis (dimethyl sulfoxide solvent, 400 MHz, chemical shift δ (ppm)):
[0062]
Embedded image
[Table 5]
Example 3 (Synthesis of tetrahydropyranylated polynuclear phenol (VIII))
In a 1 L four-necked flask, 18.9 g (0.04 mol) of 2,2′-methylenebis (6- (2,4-dihydroxyphenyl) methyl) 4-methylphenol obtained in Reference Example 3 and 60.5 g (0.72 mol) of 3,4-dihydro-2-H-pyran was charged, and 1.0 g of p-toluenesulfonic acid pyridine salt was added with stirring under ice cooling. After completion of the addition, the reaction was further carried out with stirring at the same temperature as above for 3 days, during which 80.6 g (0.96 mol) of 3,4-dihydro-2-H-pyran was further added.
[0065]
After the completion of the reaction, 1.8 g of a 20% aqueous solution of tetramethylammonium hydroxide and 50 g of water were added to the obtained reaction mixture, and the mixture was stirred and neutralized. Thereafter, the aqueous layer was separated and removed to obtain an oil layer containing the target substance. This was washed with 160 g of water. After this water washing was repeated three times, the solvent was distilled off from the oil layer by distillation under reduced pressure to obtain 44.9 g of the objective substituted polyphenol compound as a brown solid as a distillation residue. The yield based on the starting material 2,2'-methylenebis (6- (2,4-dihydroxyphenyl) methyl) 4-methylphenol was 115% (including solvent residues), and the purity by high performance liquid chromatography analysis was 77.9. %, The composition ratio of the substituted product was 50.4% for the 5-substituted product and 49.6% for the 6-substituted product.
[0066]
Proton NMR analysis (dimethyl sulfoxide solvent, 400 MHz, chemical shift δ (ppm)):
(Example of 5-substituted product)
[0067]
Embedded image
[Table 6]
Reference Example 4 (Synthesis of raw material polynuclear phenol (4))
In a 1 L four-necked flask, 87.2 g of 2,6-di (4-hydroxy-2,5-dimethylphenyl) methyl-4-methylphenol, 174.5 g of phenol, 43.6 g of methyl isobutyl ketone and p-toluene 2.7 g of sulfone was charged, and a reaction was performed for 5 hours while stirring at a temperature of 30 ° C. After completion of the reaction, the obtained reaction mixture was neutralized by adding a 16% aqueous sodium hydroxide solution, and the aqueous layer was separated and removed to obtain an oil layer containing the desired product. After washing with water, the oil layer was depressurized. After distillation, the residue was crystallized from the residual liquid and filtered to obtain 48.5 g of the target polynuclear phenol compound as a white solid. The yield based on the starting material 2,6-di (4-hydroxy-2,5-dimethylphenyl) methyl-4-methylphenol was 41%, and the purity by high performance liquid chromatography analysis was 82.7%.
[0070]
Proton NMR analysis (dimethyl sulfoxide solvent, 400 MHz, chemical shift δ (ppm)):
[0071]
Embedded image
(In the formula, the bonding position of the hydroxyl group on the benzene ring at both ends of the molecule is at the ortho position or the para position with respect to the bonding position of the methylene group.)
[0073]
[Table 7]
Example 4 (Synthesis of tetrahydropyranylated polynuclear phenol (IX))
In a 1 L four-necked flask, 41.2 g (0.07 mol) of the polynuclear phenol obtained in Reference Example 4, 3.6 g of p-toluenesulfonic acid pyridine salt, and 108 g of tetrahydrofuran were charged, and stirred at room temperature. 118 g (1.4 mol) of 3,4-dihydro-2-H-pyran were added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was further carried out with stirring at the same temperature as above for 3 days, and 118 g (1.4 mol) of 3,4-dihydro-2-H-pyran was further added during the reaction.
[0075]
After completion of the reaction, 0.5 g of a 25% aqueous solution of tetramethylammonium hydroxide and 200 g of water were added to the obtained reaction mixture, and the mixture was stirred and neutralized. Thereafter, the aqueous layer was separated and removed to obtain an oil layer containing the target substance. This was washed with 160 g of water. After repeating the water washing three times, the solvent was distilled off from the oil layer by distillation under reduced pressure to obtain 82.6 g of the objective substituted polyphenol compound as a brown solid as a distillation residue. The yield based on the starting polynuclear phenol compound was 117% (including the solvent residue), the purity by high performance liquid chromatography was 68.1%, and the composition ratio of the substituted product was 2.9% for the 3-substituted product and 25. 7% and 51.4-substituted products were 71.4%.
[0076]
Proton NMR analysis (dimethyl sulfoxide solvent, 400 MHz, chemical shift δ (ppm)):
(Example of 4-substituted product)
[0077]
Embedded image
[Table 8]
According to a preferred embodiment, the tetrahydropyranylated polynuclear phenols according to the present invention have two or more tetrahydropyranyl groups in a molecule and are useful as a sensitizer or a dissolution inhibitor in a photosensitive resin composition. .
Claims (5)
（ａ）Ｒ３ 、Ｒ８ 、Ｒ５ 及びＲ６ が水素原子であるとき、Ｒ２ 、Ｒ４ 及びＲ７ はいずれもそれぞれ独立して−ＯＲ１ 基であり（但し、Ｒ１ は上記と同じであり、４つの−ＯＲ１ 基のうち、少なくとも１つはテトラヒドロピラニル基である。）
、
（ｂ）Ｒ３ 及びＲ８ がいずれも独立して一般式（ＩＩ）
で表される基であり、Ｒ２ が−ＯＲ１ 基であるとき（但し、Ｒ１ は上記と同じであり、４つの−ＯＲ１ 基のうち、少なくとも１つはテトラヒドロピラニル基である。）、Ｒ４ 及びＲ７ は水素原子であり、Ｒ５ 及びＲ６ はメチル基であり、
（ｃ）Ｒ３ 及びＲ８ がいずれも独立してそれぞれ一般式（ＩＩＩ）
で表される基であり、Ｒ２ が−ＯＲ１ 基であるとき（但し、Ｒ１ は上記と同じであり、６つの−ＯＲ１ 基のうち、少なくとも１つはテトラヒドロピラニル基である。）、Ｒ４ 及びＲ７ は水素原子であり、Ｒ５ 及びＲ６ はメチル基であり、
（ｄ）Ｒ３ が一般式（ＩＶ）
で表される基であり、Ｒ８ が一般式（Ｖ）
で表される基であり、Ｒ４ が−ＯＲ１ 基であるとき（但し、Ｒ１ は上記と同じであり、５つの−ＯＲ１ 基のうち、少なくとも１つはテトラヒドロピラニル基である。）、Ｒ７ は水素原子であり、Ｒ２ 、Ｒ５ 及びＲ６ はメチル基である。）
で表されるテトラヒドロピラニル化多核フェノール類。General formula (I)
(A) When R 3 , R 8 , R 5 and R 6 are hydrogen atoms, R 2 , R 4 and R 7 are each independently —OR 1 groups (provided that R 1 is as defined above) it is the same, among the four -OR 1 group, at least one is a tetrahydropyranyl group.)
,
(B) R 3 and R 8 are each independently of the general formula (II)
Wherein R 2 is a —OR 1 group (provided that R 1 is the same as described above, and at least one of the four —OR 1 groups is a tetrahydropyranyl group. ), R 4 and R 7 are hydrogen atoms, R 5 and R 6 are methyl groups,
(C) R 3 and R 8 are each independently of the general formula (III)
Wherein R 2 is a —OR 1 group (provided that R 1 is the same as described above, and at least one of the six —OR 1 groups is a tetrahydropyranyl group. ), R 4 and R 7 are hydrogen atoms, R 5 and R 6 are methyl groups,
(D) R 3 is a group represented by the general formula (IV)
Wherein R 8 is a group represented by the general formula (V)
Wherein R 4 is a —OR 1 group (provided that R 1 is the same as described above, and at least one of the five —OR 1 groups is a tetrahydropyranyl group. ) And R 7 are hydrogen atoms, and R 2 , R 5 and R 6 are methyl groups. )
The tetrahydropyranylated polynuclear phenol represented by these.
で表されるテトラヒドロピラニル化多核フェノール類。General formula (IX)
The tetrahydropyranylated polynuclear phenol represented by these.
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