JPS6377871A - Novel thiophene derivative - Google Patents
Novel thiophene derivativeInfo
- Publication number
- JPS6377871A JPS6377871A JP21803886A JP21803886A JPS6377871A JP S6377871 A JPS6377871 A JP S6377871A JP 21803886 A JP21803886 A JP 21803886A JP 21803886 A JP21803886 A JP 21803886A JP S6377871 A JPS6377871 A JP S6377871A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- expressed
- methacryloyloxymethylthiophene
- thiophene derivative
- novel thiophene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000003577 thiophenes Chemical class 0.000 title claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- 229920003023 plastic Polymers 0.000 abstract description 7
- 239000004033 plastic Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- RRBBVWTUHSMDSD-UHFFFAOYSA-N thiophen-2-ylmethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CS1 RRBBVWTUHSMDSD-UHFFFAOYSA-N 0.000 abstract description 7
- ZPHGMBGIFODUMF-UHFFFAOYSA-N thiophen-2-ylmethanol Chemical compound OCC1=CC=CS1 ZPHGMBGIFODUMF-UHFFFAOYSA-N 0.000 abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- -1 methacrylic acid halide Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical class CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- LLLCSBYSPJHDJX-UHFFFAOYSA-M potassium;2-methylprop-2-enoate Chemical compound [K+].CC(=C)C([O-])=O LLLCSBYSPJHDJX-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- FUOHKPSBGLXIRL-UHFFFAOYSA-N 2-(chloromethyl)thiophene Chemical compound ClCC1=CC=CS1 FUOHKPSBGLXIRL-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- SYFOAKAXGNMQAX-UHFFFAOYSA-N bis(prop-2-enyl) carbonate;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.C=CCOC(=O)OCC=C SYFOAKAXGNMQAX-UHFFFAOYSA-N 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、下記式（Ｉ）で示される光学用プラスチック
原料として有用な新規なチオフェン誘導体に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel thiophene derivative represented by the following formula (I) that is useful as a raw material for optical plastics.
〈従来の技術〉
近年、無機光学材料に替る素材として、透明性合成樹脂
よシなる高屈折率樹脂は、その軽量性・耐衝撃性・成型
加工性・染色性が良好なことから光学用プラスチック材
料として適用分野を拡大しつつある。<Conventional technology> In recent years, high refractive index resins such as transparent synthetic resins have been used as optical plastics to replace inorganic optical materials due to their light weight, impact resistance, moldability, and dyeability. The field of application as a material is expanding.
しかし、従来の光学用プラスチック材料として用いられ
ているジエチレングリコールビスアリルカーボネート樹
脂は屈折率が１．４９〜１．５０と低いため、これから
得られる樹脂を、例えば眼鏡用レンズにすると無機光学
レンズに比較して中心層、コバ厚が大きくなる欠点があ
った。However, diethylene glycol bisallyl carbonate resin, which is used as a conventional optical plastic material, has a low refractive index of 1.49 to 1.50, so if the resin obtained from this resin is used to make lenses for eyeglasses, for example, it will be compared to inorganic optical lenses. However, there was a drawback that the thickness of the center layer and edge became large.
〈発明が解決しようとする問題点〉
以上説明したように、従来の光学用プラスチック材料は
種々の欠点を有しており改善が望まれている。そこで本
発明の目的も光学用プラスチック材料として有用な高屈
折率で透明性の優れた樹脂を与える単量体を提供するこ
とにある。<Problems to be Solved by the Invention> As explained above, conventional optical plastic materials have various drawbacks, and improvements are desired. Therefore, an object of the present invention is to provide a monomer that provides a resin with a high refractive index and excellent transparency that is useful as an optical plastic material.
〈問題点を解決するための手段〉
本発明者らは、上記目的を達成するために、検討を重ね
た結果本発明に至った。すなわち、本発明は文献未載の
前記式（Ｉ）で示される新規な糞孟北チオフェン誘導体
すなわち、２−メタクリロイルオキシメチルチオフェン
を提供する。<Means for Solving the Problems> In order to achieve the above object, the present inventors have conducted repeated studies and have arrived at the present invention. That is, the present invention provides a novel thiophene derivative represented by the formula (I) that has not been reported in any literature, that is, 2-methacryloyloxymethylthiophene.
本発明の２−メタクリロイルオキシメチルチオフェンは
、例えば、２−ヒドロキシメチルチオフェンあるいは２
−ハロゲン化メチルチオフェンとメタクリル酸誘導体と
を反応させることによって製造できる（下記式（Ｉｔ）
、佃）参照）。The 2-methacryloyloxymethylthiophene of the present invention is, for example, 2-hydroxymethylthiophene or 2-methacryloyloxymethylthiophene.
- Can be produced by reacting halogenated methylthiophene and a methacrylic acid derivative (formula (It) below)
, Tsukuda).
（但し、式中ＸはＣ１，Ｂｒまたは工、ＹはＯＨ，ＣＡ
！、ＢｒまたはＣ１〜Ｃ４のアルキル基、Ｍはアルカリ
金属をそれぞれ示す。）
すなわち、２−ヒドロキシメチルチオフェンを出発物質
として用いる場合、メタクリル酸との脱水反応によるエ
ステル化反応、メタクリル酸エステルとの脱アルコール
反応によるエステル交換反応、メタクリル酸ハライドと
の脱ハロゲン化水素によるエステル化反応を挙げること
ができる。また、２−ハロゲン化メチルチオフェンを出
発物質として用いる場合、メタクリル酸アルカリ金属塩
との脱アルカリ金属ハロゲン化物によるエステル生成反
応によシ目的物質を得ることができる。(However, in the formula, X is C1, Br or engineering, Y is OH, CA
! , Br or a C1-C4 alkyl group, and M each represents an alkali metal. ) That is, when 2-hydroxymethylthiophene is used as a starting material, esterification reaction by dehydration reaction with methacrylic acid, transesterification reaction by dealcoholization reaction with methacrylic acid ester, and esterification reaction by dehydrohalogenation with methacrylic acid halide. Examples include chemical reaction. Furthermore, when 2-halogenated methylthiophene is used as a starting material, the desired substance can be obtained through an ester-forming reaction with a dealkali metal halide with an alkali metal methacrylic acid salt.
〈発明の効果〉
本発明によって提供される前記式（１）で示される新規
なチオフェン誘導体は、置換基として重合性のメタクリ
ロイル基を有しているため、それ自体で重合させるか、
または各種のオレフィン性二重結合を有する化合物と共
重合させることによって、ポリマーやオリゴマーを得る
ことができる。そして、本発明の新規化合物を主成分と
する樹脂は高屈折率で透明性に優れているので光学用プ
ラスチックとして好適である。また、これらのポリマー
やオリゴマーは、金属やガラスとの密着性の向上剤や各
種の高分子材料としても用いることができる。<Effects of the Invention> Since the novel thiophene derivative represented by the formula (1) provided by the present invention has a polymerizable methacryloyl group as a substituent, it can be polymerized by itself or
Alternatively, polymers and oligomers can be obtained by copolymerizing with compounds having various olefinic double bonds. Since the resin containing the novel compound of the present invention as a main component has a high refractive index and excellent transparency, it is suitable as an optical plastic. Furthermore, these polymers and oligomers can also be used as adhesion improvers with metals and glass, and as various polymeric materials.
〈実施例〉 以下、本発明を実施例によυ具体的に説明する。<Example> Hereinafter, the present invention will be specifically explained with reference to Examples.
実施例１
撹拌機、温度計、ジムロート型冷却管および滴下漏斗を
備えた容量ａｏｏｍ／のガラス製フラスコに、２−ヒド
ロキシメチルチオフェン９．ＩＮ、）ジエチルアミン１
６．１，９．クロロホルム１００Ｍおよびフェノチアジ
ン０．０１０ｇを仕込んだ。次いで、内温を２０〜３０
℃に保ち撹拌を続けながらメタクリル酸クロライド１２
．５ｇを２０分間で滴下した。滴下終了後頁に同温度で
１２０分間撹拌を続けた後反応液を水、希塩酸、水、炭
酸ナトリウム水溶液、水の順に洗浄した。得られた有機
層を無水硫酸ナトリウムを加え、乾燥した後、クロロホ
ルムを減圧留去し、２−メタクリロイルオキシメチルチ
オフェンを得た。得られたエステルを減圧蒸留によって
Ｎ製した。沸点８７〜８８℃／１、５〜２．０ ｖＭｇ
、収−Ｊｌｘｏ、９．ｌ収率７ｓ、ｏ％）。Example 1 2-Hydroxymethylthiophene 9.0% was added to a glass flask with a capacity of aoom/a, equipped with a stirrer, a thermometer, a Dimroth condenser, and an addition funnel. IN,) diethylamine 1
6.1, 9. 100M of chloroform and 0.010 g of phenothiazine were charged. Next, reduce the internal temperature to 20-30
methacrylic acid chloride 12 while keeping it at ℃ and continuing stirring.
．． 5 g was added dropwise over 20 minutes. After the addition was completed, stirring was continued for 120 minutes at the same temperature, and the reaction solution was washed with water, diluted hydrochloric acid, water, aqueous sodium carbonate, and water in this order. After adding anhydrous sodium sulfate to the obtained organic layer and drying it, chloroform was distilled off under reduced pressure to obtain 2-methacryloyloxymethylthiophene. The obtained ester was distilled under reduced pressure to produce N. Boiling point 87-88℃/1, 5-2.0 vMg
, Collection-Jlxo, 9. l yield 7s, o%).
得られたエステルは無色の液体であった。The resulting ester was a colorless liquid.
次に得られたこの新規物質の構造決定のための分析結果
を示す。Next, we will show the analysis results for determining the structure of this new substance.
Ｏ沸 点 ８７〜ｂ
Ｏ元素分析値
Ｃ（係） Ｈ（係） Ｓ（係）理論値 ５
９．３２ ５．５３ １７．５９分析値 ５９
．４１ ５．５０ １７．７２０質量分析スペク
トル
ＥＩ ｍ／ｅ＝１８２ （Ｍつ
Ｏ’Ｈ−ＮＭＲ（溶媒： ＣｒＸ：：Ｉｓ 、内ｓｉ準
動物質ＴＭＳ）−５，３３／／ ２Ｈ−ＣＨ，−
−１，９５Ｎ ３ＨＣＨ，−
ＯｌＲ
１７２０ｃｒｒＬ−’ エステル ｖ ＞ｃ
ｘ。O boiling point 87~b O elemental analysis value C (section) H (section) S (section) theoretical value 5
9.32 5.53 17.59 Analysis value 59
．． 41 5.50 17.720 Mass spectrometry spectrum EI m/e = 182 (M2O'H-NMR (solvent: CrX::Is, si quasi-animal TMS) -5,33//2H-CH, - -1,95N 3HCH, -OlR 1720crrL-' Ester v > c
x.
１６３５ ｃｍ−’ オレフィン ν ＞ｃ−
ｃ＜１１５０〜１１５５ｃｒＩＬ”−１チオフェン骨格
なお、この赤外線吸収スペクトルを第１図に示す。1635 cm-' Olefin ν >c-
c<1150-1155crIL''-1 Thiophene skeleton This infrared absorption spectrum is shown in FIG.
実施例２
実施例１と同様の装置に２−クロロメチルチオフェン１
３．３ｇ、メタクリル酸カリウム１３．７＃およびジメ
チルスルホキシド２００−を仕込んだ。Example 2 2-chloromethylthiophene 1 was added to the same apparatus as in Example 1.
3.3 g of potassium methacrylate, 13.7 # of potassium methacrylate, and 200 # of dimethyl sulfoxide were charged.
次いで撹拌しなから内温５５〜６０℃で５時間反応させ
た。反応溶液を０．３ Ｎ−ＨＣｌ １０００ｄ中に加
え、ジエチルエーテル２００ Ｒ１で３回抽出した。Next, the mixture was reacted for 5 hours at an internal temperature of 55 to 60° C. without stirring. The reaction solution was added to 0.3 N HCl 1000d and extracted three times with diethyl ether 200 R1.
エーテル層を洗浄した後無水硫酸す） ＩＪウムで乾燥
した。エーテルを留去し、２−メタクリロイルオキシメ
チルチオフェンを得た。得られたエステルを減圧蒸留に
よって精製した。得られた新規物質の構造決定のための
分析結果は実施例１と同じであった。After washing the ether layer, it was dried with anhydrous sulfuric acid and IJum. Ether was distilled off to obtain 2-methacryloyloxymethylthiophene. The resulting ester was purified by vacuum distillation. The analysis results for determining the structure of the obtained new substance were the same as in Example 1.
第１図は本発明にかかる２−メタクリロイルオキシメチ
ルチオフェンのＮａ Ｃ１板上における赤外線吸収スペ
クトルを示す図である。FIG. 1 is a diagram showing an infrared absorption spectrum of 2-methacryloyloxymethylthiophene according to the present invention on a Na C1 plate.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21803886A JPS6377871A (en) | 1986-09-18 | 1986-09-18 | Novel thiophene derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21803886A JPS6377871A (en) | 1986-09-18 | 1986-09-18 | Novel thiophene derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6377871A true JPS6377871A (en) | 1988-04-08 |
Family
ID=16713670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21803886A Pending JPS6377871A (en) | 1986-09-18 | 1986-09-18 | Novel thiophene derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6377871A (en) |
-
1986
- 1986-09-18 JP JP21803886A patent/JPS6377871A/en active Pending
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