JP4925524B2 - Bis (halogen-substituted phenylthio) fluorene compound and method for producing the same - Google Patents
Bis (halogen-substituted phenylthio) fluorene compound and method for producing the same Download PDFInfo
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- JP4925524B2 JP4925524B2 JP2001208923A JP2001208923A JP4925524B2 JP 4925524 B2 JP4925524 B2 JP 4925524B2 JP 2001208923 A JP2001208923 A JP 2001208923A JP 2001208923 A JP2001208923 A JP 2001208923A JP 4925524 B2 JP4925524 B2 JP 4925524B2
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- halogen
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- fluorene compound
- substituted phenylthio
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- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title claims description 14
- -1 fluorene compound Chemical class 0.000 title claims description 13
- 125000003356 phenylsulfanyl group Chemical class [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical class SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 12
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000004734 Polyphenylene sulfide Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920000069 polyphenylene sulfide Polymers 0.000 description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229920006015 heat resistant resin Polymers 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VZXOZSQDJJNBRC-UHFFFAOYSA-N 4-chlorobenzenethiol Chemical compound SC1=CC=C(Cl)C=C1 VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- NQXNYVAALXGLQT-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C1(C=2C=CC(OCCO)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 NQXNYVAALXGLQT-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- AQWJSSDPSYJFSR-UHFFFAOYSA-N C1C2=CC=CC=C2C3=C1C(=C(C=C3)SC4=CC=CC=C4Cl)SC5=CC=CC=C5Cl Chemical compound C1C2=CC=CC=C2C3=C1C(=C(C=C3)SC4=CC=CC=C4Cl)SC5=CC=CC=C5Cl AQWJSSDPSYJFSR-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052740 iodine Inorganic materials 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
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000638 solvent extraction Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明はビス（ハロゲン置換フェニルチオ）フルオレン化合物及びその製造方法に関する。
【０００２】
【従来の技術】
ビスフェノールフルオレンやビスフェノキシエタノールフルオレン等のフルオレン骨格を有する化合物は、耐熱性が高い、高屈折率である、低誘電率である、収縮率が小さい、難燃性であるといった特長を有しており、光・電子樹脂材料用途や耐熱樹脂材料用途のポリエステルやエポキシ樹脂の原料として用いられている。また、クロロベンゼン等の芳香族ハロゲン化合物はポリフェニレンサルファイド（ＰＰＳ）等の樹脂原料や、ハロゲン系難燃剤等の樹脂添加剤として用いられている。しかしながら、上記に示したようなフルオレン骨格を有する化合物は、耐熱樹脂用途や光・電子樹脂材料用途として用いるためには、耐熱温度、屈折率向上の点で、さらなる改善が望まれている。また、ＰＰＳについては耐熱性の向上や低収縮率についての改善が望まれており、ハロゲン系難燃剤については難燃性の向上が望まれている。
【０００３】
【発明が解決しようとする課題】
本発明は、耐熱樹脂用途や光・電子樹脂材料用途、ＰＰＳ樹脂原料、難燃剤などの用途に適しており、耐熱性、高屈折率材料として優れた性能を有する新規なフルオレン化合物及びその製造方法を提供することを目的とする。
【０００４】
【課題を解決するための手段】
本発明は、以下のビス（ハロゲン置換フェニルチオ）フルオレン化合物及びその製造方法に関する。
項１ 一般式（Ｉ）
【０００５】
【化３】
〔式中、Ｒ1、Ｒ2、Ｒ3及びＲ4は、同一又は異なって、水素原子又はＣ１〜Ｃ６の直鎖状乃至分岐状のアルキル基を示し、Ｘはハロゲン原子を示す。ｎは、０〜１０の整数を示す。〕
で表されることを特徴とするビス（ハロゲン置換フェニルチオ）フルオレン化合物。
項２ Ｒ1、Ｒ2、Ｒ3及びＲ4が水素原子、Ｘが塩素原子であり、ｎが０である項１に記載のビス（ハロゲン置換フェニルチオ）フルオレン化合物。
項３ 酸性条件下でフルオレノン（１）とハロゲン置換フェニルチオール類（２）及び（３）とを反応させることを特徴とする一般式（Ｉ）で表されるビス（ハロゲン置換フェニルチオ）フルオレン化合物の製造方法。
【０００７】
【化４】
〔式中、Ｒ1、Ｒ2、Ｒ3及びＲ4は、同一又は異なって、水素原子又はＣ１〜Ｃ６の直鎖状乃至分岐状のアルキル基を示し、Ｘはハロゲン原子を示す。ｎは、０〜１０の整数を示す。〕
項４ 反応温度を１０℃以下として反応させることを特徴とする項３に記載のビス（ハロゲン置換フェニルチオ）フルオレン化合物の製造方法。
【０００９】
【発明の実施の形態】
本発明において、Ｃ１〜Ｃ６アルキル基としては、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、ペンチル、ヘキシルなどの直鎖または分枝を有するアルキル基が挙げられる。
【００１０】
ｎは０〜１０で、好ましくは０〜６程度で、さらに好ましくは０〜２である。
【００１１】
Ｘとしては、塩素原子、フッ素原子、臭素原子、ヨウ素原子などのハロゲン原子が挙げられる。
【００１２】
一般式（Ｉ）で示される化合物としては、Ｒ1、Ｒ2、Ｒ3及びＲ4がいずれも水素原子で、Ｘが塩素原子であり、ｎが０又は１の化合物が好ましい。
【００１３】
より具体的には、ビス（クロロフェニルチオ）フルオレンが好ましい化合物として挙げられる。
【００１４】
一般式（Ｉ）で示される化合物は、下記の＜反応工程式＞に従って製造することができる。
＜反応工程式＞
【００１５】
【化５】
〔式中、Ｒ1、Ｒ2、Ｒ3及びＲ4、Ｘ、及びｎは、上記に定義した通りである。〕
反応は、溶媒の存在下でも無溶媒でも可能であるが、溶媒を用いる場合は、トルエン、キシレン、ベンゼンなどの芳香族炭化水素を用いることができる。溶媒の使用量は、特に限定されず適宜設定することができるが、通常、フルオレノン（１）１ｇに対して０．１〜５０ｍｌ程度である。反応の雰囲気としては、窒素、アルゴン等の不活性ガス雰囲気が好ましい。反応はフルオレノン化合物（１）１モルに対しハロゲン置換フェニルチオール類（２）及び（３）を合わせて２〜４モル程度用いて、酸として硫酸、塩酸、塩酸ガス、ｐ−トルエンスルホン酸、メタンスルホン酸などを適量（例えば、フルオレノン１モルに対して０．０５〜１００モル程度）使用して行うことができる。反応温度は、通常８０℃以下であり、反応温度としては室温以下が好ましく、１０℃以下がさらに好ましい。反応温度の下限は特に限定されるものではないが、通常−２０℃程度である。反応時間は、原料の使用量に応じて適宜設定できるが、通常０．５〜１２時間程度である。式（２）で表されるハロゲン置換フェニルチオール類は、公知の物質であり、容易に入手可能である。
【００１７】
反応生成物である一般式（Ｉ）の化合物は、通常の分離、精製手段、例えば再結晶、溶媒抽出法、カラムクロマトグラフィー法等を用いて、容易に単離、精製することができる。
【００１８】
【発明の効果】
本発明の化合物は、分子中にハロゲン原子を有しており、また硫黄原子を分子骨格に有しているので、従来のハロゲン原子や硫黄原子を分子中に有しないビスフェノールフルオレン類よりも耐熱性が高く、高屈折率であり、低誘電率であり、収縮率が小さく、難燃性が高い。また、フルオレン骨格を有していることからポリフェニレンサルファイド（ＰＰＳ）等の樹脂原料として耐熱性の向上や低収縮率についての改善に効果的であり、ハロゲン系難燃剤として用いた場合の難燃性向上に効果的である。
【００１９】
【実施例】
次に実施例により本発明をさらに詳細に説明するが、本発明はこれら実施例によって何ら限定されるものではない。
【００２０】
実施例１
３Ｌの４つ口フラスコをアルゴン雰囲気とし、フルオレノン２０２ｇ、ｐ−クロロチオフェノール４８５ｇ、トルエン１３００ｍｌを加えて、容器内を０℃に保持して攪拌し、濃硫酸１００ｍｌを加えて４時間反応させた。その後、１１００ｍｌの蒸留水を滴下して、濾過し、固形分１７１ｇをアセトン８００ｍｌで再結晶して、固形分を乾燥し、生成物１６２ｇを得た。得られた生成物の液体クロマトグラフィーによる純度は９９．６％であった。分析結果を、下記に、及び図１〜４に示す。
MSスペクトル
分子イオンピーク；M/Z＝４５０
赤外線吸収スペクトル
フルオレン骨格振動：1445,743cm-1付近
ベンゼン環骨格
3000cm-1付近 芳香族C-H伸縮振動
1800〜1950cm-1付近 倍音帯
1571,1473cm-1 骨格振動
パラ置換ベンゼンCH面外変角振動：1184,1080,1030,1014,825cm-1
Ph-ClのC-Cl伸縮振動：1091cm-1
1H-NMR（重クロロホルム溶媒、270MHz）スペクトル
7.0〜7.5ppm：芳香族のピーク
7.0ppm一重線：4-クロロチオフェノールのピーク
13C-NMR（重クロロホルム溶媒、270MHz）スペクトル
67.1ppm：フルオレン９位の４級炭素のピーク
120〜145ppm：芳香族炭素のピーク
【図面の簡単な説明】
【図１】 実施例１で得られた化合物のＭＳスペクトルを示す図である。
【図２】 実施例１で得られた化合物の赤外線吸収スペクトルを示す図である。
【図３】 実施例１で得られた化合物の1Ｈ−NMRのスペクトルを示す図である。
【図４】 実施例１で得られた化合物の13Ｃ−NMRのスペクトルを示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a bis (halogen-substituted phenylthio) fluorene compound and a method for producing the same.
[0002]
[Prior art]
Compounds having a fluorene skeleton such as bisphenol fluorene and bisphenoxyethanol fluorene have features such as high heat resistance, high refractive index, low dielectric constant, low shrinkage, and flame retardancy, It is used as a raw material for polyester and epoxy resins for optical and electronic resin materials and heat-resistant resin materials. Aromatic halogen compounds such as chlorobenzene are used as resin materials such as polyphenylene sulfide (PPS) and resin additives such as halogen flame retardants. However, in order to use the compound having a fluorene skeleton as described above as a heat-resistant resin application or an optical / electronic resin material application, further improvement is desired in terms of an increase in heat-resistant temperature and refractive index. In addition, improvement in heat resistance and low shrinkage are desired for PPS, and improvement in flame retardancy is desired for halogen-based flame retardants.
[0003]
[Problems to be solved by the invention]
The present invention is suitable for applications such as heat-resistant resin applications, optical / electronic resin material applications, PPS resin raw materials, flame retardants, and the like, and a novel fluorene compound having excellent performance as a heat-resistant and high-refractive index material, and a method for producing the same The purpose is to provide.
[0004]
[Means for Solving the Problems]
The present invention relates to the following bis (halogen-substituted phenylthio) fluorene compounds and methods for producing the same.
[0005]
[Chemical 3]
[Wherein, R 1 , R 2 , R 3 and R 4 are the same or different and each represents a hydrogen atom or a C 1 to C 6 linear or branched alkyl group, and X represents a halogen atom. n shows the integer of 0-10. ]
A bis (halogen-substituted phenylthio) fluorene compound represented by the formula:
Item 2 The bis (halogen-substituted phenylthio) fluorene compound according to
Item 3 A bis (halogen-substituted phenylthio) fluorene compound represented by the general formula (I) characterized by reacting fluorenone (1) with halogen-substituted phenylthiols (2) and (3) under acidic conditions Production method.
[0007]
[Formula 4]
[Wherein, R 1 , R 2 , R 3 and R 4 are the same or different and each represents a hydrogen atom or a C 1 to C 6 linear or branched alkyl group, and X represents a halogen atom. n shows the integer of 0-10. ]
Item 4 The method for producing a bis (halogen-substituted phenylthio) fluorene compound according to
[0009]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the C 1 -C 6 alkyl group has a straight chain or branched chain such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl and the like. An alkyl group is mentioned.
[0010]
n is 0 to 10, preferably about 0 to 6, and more preferably 0 to 2.
[0011]
Examples of X include halogen atoms such as chlorine atom, fluorine atom, bromine atom and iodine atom.
[0012]
As the compound represented by the general formula (I), a compound in which R 1 , R 2 , R 3 and R 4 are all hydrogen atoms, X is a chlorine atom and n is 0 or 1 is preferable.
[0013]
More specifically, bis (chlorophenylthio) fluorene is mentioned as a preferred compound.
[0014]
The compound represented by the general formula (I) can be produced according to the following <Reaction Process Formula>.
<Reaction process formula>
[0015]
[Chemical formula 5]
[Wherein R 1 , R 2 , R 3 and R 4 , X, and n are as defined above. ]
The reaction can be carried out in the presence or absence of a solvent, but when a solvent is used, an aromatic hydrocarbon such as toluene, xylene, benzene or the like can be used. Although the usage-amount of a solvent is not specifically limited, Although it can set suitably, Usually, it is about 0.1-50 ml with respect to 1 g of fluorenone (1). As the reaction atmosphere, an inert gas atmosphere such as nitrogen or argon is preferable. The reaction uses about 2 to 4 moles of halogen-substituted phenylthiols (2) and (3) per mole of fluorenone compound (1), and sulfuric acid, hydrochloric acid, hydrochloric acid gas, p-toluenesulfonic acid, methane are used as acids. A suitable amount (for example, about 0.05 to 100 moles per mole of fluorenone) can be used. The reaction temperature is usually 80 ° C. or lower, and the reaction temperature is preferably room temperature or lower, more preferably 10 ° C. or lower. Although the minimum of reaction temperature is not specifically limited, Usually, it is about -20 degreeC. Although reaction time can be suitably set according to the usage-amount of a raw material, it is about 0.5 to 12 hours normally. Halogen-substituted phenylthiols represented by the formula (2) are known substances and are easily available.
[0017]
The compound of the general formula (I), which is a reaction product, can be easily isolated and purified using conventional separation and purification means such as recrystallization, solvent extraction, column chromatography and the like.
[0018]
【Effect of the invention】
Since the compound of the present invention has a halogen atom in the molecule and also has a sulfur atom in the molecular skeleton, it has higher heat resistance than conventional bisphenolfluorenes having no halogen atom or sulfur atom in the molecule. , High refractive index, low dielectric constant, small shrinkage, and high flame retardancy. In addition, since it has a fluorene skeleton, it is effective in improving heat resistance and low shrinkage as a resin raw material such as polyphenylene sulfide (PPS), and flame retardancy when used as a halogen-based flame retardant It is effective for improvement.
[0019]
【Example】
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples.
[0020]
Example 1
A 3 L four-necked flask was placed in an argon atmosphere, 202 g of fluorenone, 485 g of p-chlorothiophenol and 1300 ml of toluene were added, the container was stirred at 0 ° C., and 100 ml of concentrated sulfuric acid was added and reacted for 4 hours. . Thereafter, 1100 ml of distilled water was added dropwise and filtered, and 171 g of solid content was recrystallized from 800 ml of acetone, and the solid content was dried to obtain 162 g of product. The purity of the obtained product by liquid chromatography was 99.6%. The analysis results are shown below and in FIGS.
MS spectrum molecular ion peak; M / Z = 450
Infrared absorption spectrum fluorene skeleton vibration: benzene ring skeleton around 1445,743 cm -1
Around 3000cm -1 Aromatic CH stretching vibration
1800 ~ 1950cm -1 Near harmonic
1571,1473cm -1 Skeletal vibration Para-substituted benzene CH Out-of-plane variable angular vibration: 1184,1080,1030,1014,825cm -1
Ph-Cl C-Cl stretching vibration: 1091 cm -1
1 H-NMR (deuterated chloroform solvent, 270 MHz) spectrum
7.0-7.5ppm: Aromatic peak
7.0ppm singlet: peak of 4-chlorothiophenol
13 C-NMR (deuterated chloroform solvent, 270 MHz) spectrum
67.1ppm: Peak of quaternary carbon at 9th position of fluorene
120-145ppm: Aromatic carbon peak [Brief description of drawings]
1 is a graph showing an MS spectrum of the compound obtained in Example 1. FIG.
2 is a graph showing an infrared absorption spectrum of the compound obtained in Example 1. FIG.
3 is a diagram showing the 1 H-NMR spectrum of the compound obtained in Example 1. FIG.
4 is a 13 C-NMR spectrum of the compound obtained in Example 1. FIG.
Claims (4)
フルオレノン（１）とハロゲン置換フェニルチオール類（２）とを、
反応温度を１０℃以下として反応させることを特徴とする、
一般式（Ｉ）で表されるビス（ハロゲン置換フェニルチオ）フルオレン化合物の製造方法。
Fluorenone (1) with a halogen-substituted phenyl thiols and (2),
The reaction is performed at a reaction temperature of 10 ° C. or lower ,
A method for producing a bis (halogen-substituted phenylthio) fluorene compound represented by the general formula (I).
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