JPS6377872A - Novel brominated thiophene derivative - Google Patents
Novel brominated thiophene derivativeInfo
- Publication number
- JPS6377872A JPS6377872A JP21803986A JP21803986A JPS6377872A JP S6377872 A JPS6377872 A JP S6377872A JP 21803986 A JP21803986 A JP 21803986A JP 21803986 A JP21803986 A JP 21803986A JP S6377872 A JPS6377872 A JP S6377872A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- expressed
- brominated
- compound
- oligomers
- 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 abstract description 8
- 239000000126 substance Substances 0.000 claims description 5
- -1 methacryloyl group Chemical group 0.000 abstract description 10
- 230000003287 optical effect Effects 0.000 abstract description 10
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- 239000004033 plastic Substances 0.000 abstract description 8
- 229920003023 plastic Polymers 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011521 glass Substances 0.000 abstract description 3
- 239000003063 flame retardant Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 125000001424 substituent group Chemical group 0.000 abstract description 2
- 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 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229950005228 bromoform Drugs 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- 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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-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
- 238000004440 column chromatography Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- IXULCOYQSDIBFO-UHFFFAOYSA-N (3-bromothiophen-2-yl)methanol Chemical compound OCC=1SC=CC=1Br IXULCOYQSDIBFO-UHFFFAOYSA-N 0.000 description 1
- QLDZVWZKGGKDOI-UHFFFAOYSA-N (3-bromothiophen-2-yl)methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=1SC=CC=1Br QLDZVWZKGGKDOI-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 150000001340 alkali metals 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
- 238000001816 cooling Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 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
- 239000000178 monomer Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- LLLCSBYSPJHDJX-UHFFFAOYSA-M potassium;2-methylprop-2-enoate Chemical compound [K+].CC(=C)C([O-])=O LLLCSBYSPJHDJX-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (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（１）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臭素化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 brominated thiophene derivative useful as a raw material for optical plastics represented by the following formula (1).
（但し、式中ｎは１または２を示す。）〈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。(However, in the formula, n represents 1 or 2.) <Prior art> In recent years, high refractive index resins such as transparent synthetic resins have been used as materials to replace inorganic optical materials due to their light weight, impact resistance, Due to its good moldability and dyeability, its application as an optical plastic 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厚、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 have a lower refractive index than inorganic optical lenses. However, there was a drawback that the center thickness and edge thickness 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Ｆ
ｉ種々の欠点を有しておシ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, the conventional optical plastic material F
It has 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、検肘を重ね
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（１）で示される新規な臭素化チオフェン誘導
体を提供する。<Means for Solving the Problems> In order to achieve the above object, the present inventors conducted repeated elbow tests, and as a result, arrived at the present invention. That is, the present invention provides a novel brominated thiophene derivative represented by the formula (1) that has not been described in any literature.
本発明Ｋかかる新規な臭素化チオフェン誘導体として、
具体的には、３−ブロモ−２−メタクリロイルオキシメ
チルチオフェン、５−ブロモ−２−メタクリロイルオキ
シメチルチオフェン、３，４−ジブロモ−２−メタクリ
ロイルオキシチオフェン、３，５−ジブロモ−２−メタ
クリロイルオキシメチルチオフェン、４，５−ジブロモ
−２−メタクリロイルオキシメチルチオフェン等を挙げ
ることができる。As such novel brominated thiophene derivatives of the present invention,
Specifically, 3-bromo-2-methacryloyloxymethylthiophene, 5-bromo-2-methacryloyloxymethylthiophene, 3,4-dibromo-2-methacryloyloxythiophene, 3,5-dibromo-2-methacryloyloxymethyl Examples include thiophene, 4,5-dibromo-2-methacryloyloxymethylthiophene, and the like.
前記式（りで示される新規な臭素化チオフェン誘導体は
、例えば臭素化−２−ヒドロキシメチルチオフェンある
いは臭素化−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（ｎ）、（２）参照）。The novel brominated thiophene derivative represented by the above formula (R) can be produced, for example, by reacting brominated-2-hydroxymethylthiophene or brominated-2-halogenated methylthiophene with a methacrylic acid derivative (
(See formulas (n) and (2) below).
（但し、式中ｎ＃：ｔ１または２、ＸはＣ１％Ｂｒまた
は工、Ｙ ｔｄ ＯＨ，ＣＩ、 Ｂｒ ”！ タｈ Ｃ
，〜Ｃ，Ｏ７ルキ）Ｌｔ基、Ｍはアルカリ金属をそれぞ
れを示す。）すなわち、臭素化−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ょ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、臭素化−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υ目的物質を得る
ことができる。(However, in the formula, n#: t1 or 2, X is C1%Br or
, ~C, O7) Lt group, M each represents an alkali metal. ) That is, when brominated-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 dehalogenation reaction with methacrylic acid halide. An example of this is an esterification reaction using hydrogen chloride. Furthermore, when brominated-2-halogenated methylthiophene is used as a starting material, the target substance υ can be obtained by an ester-forming reaction with a dealkali metal halide with an alkali metal methacrylate salt.
〈発明の効果〉
本発明によって提供される前記式（りで示される新規な
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、側鎖に臭素化されたチオフェン
環を持つ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剤
マーは、金属やガラスとの密着性の向上〆や樹脂の難燃
化剤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 above formula (R) provided by the present invention has a polymerizable methacryloyl group as a substituent, it can be polymerized by itself or combined with various olefins. Polymers and oligomers with brominated thiophene rings in side chains can be obtained by copolymerizing with compounds having a double bond.The resins containing the novel compounds of the present invention as main components have high refractive index. These polymers and oligomers are suitable as optical plastics due to their excellent transparency and transparency.In addition, these polymers and oligomers can be used to improve adhesion to metals and glass, and as flame retardants for resins. can.
〈実施例〉 以下、本発明を実施例によシ具体的に説明する。<Example> Hereinafter, the present invention will be specifically explained using examples.
実施例１
撹拌機、温度計、ジムロート型冷却管及び滴下漏斗を備
えた容！３００ｍのガラス製フラスコに、２−ブロモメ
チルジブロモチオフェン３８．０ｇ、メタクリル酸カリ
ウム１３．９．９．ジメチルスルホキシドｚｏｏｍｔお
よびフェノチアジン０．０２，９を仕込んだ。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 −Ｈ−ＨＣ１）Ｏ００中にあけ、
ジエチルエーテル２００ｒｎｌで３回抽出した。エーテ
ル層を水、水酸化ナトリウム水溶液、水の順で洗浄し、
得られたエーテル層を無水硫酸ナトリウムで乾燥した。Example 1 A vessel equipped with a stirrer, thermometer, Dimroth cooling tube and addition funnel! In a 300 m glass flask, 38.0 g of 2-bromomethyldibromothiophene and 13.9.9 g of potassium methacrylate were added. Charged with dimethyl sulfoxide zoomt and phenothiazine 0.02.9. Then,
The reaction was allowed to proceed for 5 hours at an internal temperature of 55 to 60° C. without stirring. Pour the reaction solution into 0.3 N -H-HC1)O00,
Extracted three times with 200 rnl of diethyl ether. The ether layer was washed with water, an aqueous sodium hydroxide solution, and water in that order.
The obtained ether layer was dried over anhydrous sodium sulfate.
エーテルを留去し、生成したエステルを減圧蒸留した。The ether was distilled off, and the resulting ester was distilled under reduced pressure.
沸点１）３〜１）４℃１０．８〜１．０寵ｉ（ｇ、収！
−２１，１ｇ（収率５６．３係、３，４−ジブロモ体１
８．７％、３．５−ジブロモ体４８．４１））、４，５
−ジブロモ体３２．９％）。得られたエステルをカラム
クロマトグラフィーにより単離、精製した。Boiling point 1) 3~1) 4℃ 10.8~1.0g (g, yield!
-21,1g (yield 56.3%, 3,4-dibromo form 1
8.7%, 3.5-dibromo form 48.41)), 4,5
- dibromo form (32.9%). The obtained ester was isolated and purified by column chromatography.
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.
＜３，４−ジブロモ体〉
０元素分析値
Ｃ（％） Ｈ（％） Ｓ （％） Ｂｒ
（％）理論値 ３１．７９ ２．３７ ９．４３
４７．００分析値 ３２．８８ ２．２９
９．０８ ４７．４３Ｑ質量分析スペクトル
ＥＩ ｍ／ｅ ＝ ３３８，３４０，３４２（Ｍ＋）
０ ’Ｈ−ＮＦａ （溶媒；ＣＤｔＪｓ 内部標準物
ｇ；ＴＭＳ）δ■７．２ｐｐｌＩＨチオフェン環
婁５．２３四 ２Ｈ−ＣＨ，−
−１，９５μ ｓＨＣＨ，−
ｏ ＩＲ１７３０ａｒｉ−’ エステ／Ｌ／ Ｉ
／ ＞Ｃ＝ｌｌＯ１６２０ｃｎＬ−’ オレフ
ィン ！／＞ｃ−ｃ＜１）５０〜１）５５α−１チオフ
ェン骨格＜３，５−ジブロモ体〉
０元素分析値
Ｃ（％） ＩＩ （％） Ｓ（％）Ｂｒ（Ｌ：ｌ
））理論値 ３１．７９ ２．３７ ９．４３
４７．００分析値 ３２．７０ ２．４１ ９
．１０ ４７．０９０質量分析スペクトル
ＥＩ ｍ／ｅ ＝ ３３８ 、３４０．３４２
（Ｍ ）０ ’Ｈ−ＮＭＲ（溶媒；ＣＤＣ１，内部
標準物質；ＴＭＳ）δ−７，０ＩｌｌｐｌＩＨチオフェ
ン環−５，２３清 ２Ｈ−ＣＨ，−
■１．９５ｐｌＩｌ ３ＨＣＨ，−ｏＩＲ１７３０
ａｎ−’ エステル ν ＞ｃｍ。<3,4-dibromo form> 0 elemental analysis value C (%) H (%) S (%) Br
(%) Theoretical value 31.79 2.37 9.43
47.00 Analysis value 32.88 2.29
9.08 47.43Q Mass spectrometry spectrum EI m/e = 338,340,342 (M+)
0 'H-NFa (solvent; CDtJs internal standard g; TMS) δ 7.2 ppl IH thiophene ring 5.234 2H-CH, - -1,95μ sHCH, - o IR1730ari-' Este/L/I
/ >C=llO1620cnL-' Olefin! //cc<1) 50~1) 55α-1 thiophene skeleton <3,5-dibromo form> 0 elemental analysis value C (%) II (%) S (%) Br (L:l
)) Theoretical value 31.79 2.37 9.43
47.00 Analysis value 32.70 2.41 9
．． 10 47.090 Mass spectrometry spectrum EI m/e = 338, 340.342
(M)0'H-NMR (solvent: CDC1, internal standard: TMS) δ-7,0IllplIH thiophene ring-5,23 pure 2H-CH,- ■1.95plIl 3HCH, -oIR1730
an-' ester ν>cm.
１６２０ａｎ−’ オンフィン ν ＞ｃ−ｃ＜
１）５０〜１）５５ｍ−” チオフェン骨格＜４，５
−ジブロモ体〉
軸素８析ｆＥ Ｃ（％） Ｈ（％） Ｓ（％）Ｂ・（
係）理論値 ３１．７９ ２．３７ ９．４３ ４
７．００分析値 ３２．９２ ２．５０ ９．１３
４６．９９ｏＪｘ量分析スペクトル
ＥＩ ｍ／ｅ ＝ ３３８．３４０．３４２ （Ｍ
”）０ ’Ｈ−ＮＭＲ（溶媒；ｃＤＣｚ、 内部標
準物質；ＴＭＳ）δ−６，９μ ＩＨチオフェン還
御５．２３窄 ２Ｈ−ＣＨ，−
−１，９５四 ３ＨＣＨ，−
ＱＩＲ１７３０儒−１エステル ν 〉Ｃ−０１６２
０ＯｒＩＬ−’ オレフィン ν ＞ｃｘｃ＜
１）５０〜１）５５ ｃｍ−’ チオフェン環なお、
３，５−ジブロモ体の赤外線吸収スペクトルを第１図に
示す。1620an-'onfin ν >c-c<
1) 50-1) 55m-” Thiophene skeleton <4,5
-Dibromo body> Axial element 8 analysis fE C (%) H (%) S (%) B・(
) Theoretical value 31.79 2.37 9.43 4
7.00 Analysis value 32.92 2.50 9.13
46.99oJx quantity analysis spectrum EI m/e = 338.340.342 (M
”)0'H-NMR (solvent: cDCz, internal standard: TMS) δ-6,9μ IH thiophene reduction 5.23% 2H-CH, - -1,954 3HCH, - QIR1730 F-1 ester ν 〉 C-0162
0OrIL-' Olefin ν >cxc<
1) 50 to 1) 55 cm-' Thiophene ring,
The infrared absorption spectrum of 3,5-dibromo compound is shown in FIG.
実施例２
実施例１と同様の装置にモノブロモ−２−ヒドロキシメ
チルチオフェン（３−ブロモ体３０ｉｉ係、５−ブロモ
体７０重ｆ％）１９．３ｇ、トリエチルアミン２０．２
１．クロロホルム２００ｄおよびフェノチアジン０．０
１３．９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グリル酸クロライド１８．８＃
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、クロロホルムを減圧
留去した後、生成したエステルを減圧蒸留した。沸点１
）９〜１２１℃／ １．５〜２．０ ｗＩＩＨｇｏ収量
１６．５＆（収率６３．１％；３−ブロモ体１９．９％
、５−ブロモ体ｓ ｏ、 １％ ）。得られたエステル
をカラムクロマトグラフィーによシ単離、精製した。Example 2 Into the same apparatus as in Example 1, 19.3 g of monobromo-2-hydroxymethylthiophene (30 ii of 3-bromo form, 70 wt% of 5-bromo form) and 20.2 g of triethylamine were added.
1. Chloroform 200d and phenothiazine 0.0
I prepared 13.9. Next, while keeping the internal temperature at 20 to 30°C and continuing stirring, add 18.8# of metaglylic acid chloride.
was added dropwise over 20 minutes. After finishing dropping, apply 120 ml at the same temperature to the page.
After continuing to stir for a minute, the reaction solution was washed with water, diluted hydrochloric acid, water, aqueous sodium carbonate, and water in this order. The obtained organic layer was dried by adding anhydrous sodium sulfate, chloroform was distilled off under reduced pressure, and the generated ester was distilled under reduced pressure. boiling point 1
)9-121℃/1.5-2.0 wIIHgo yield 16.5 & (yield 63.1%; 3-bromo form 19.9%
, 5-bromo SO, 1%). The obtained ester was isolated and purified by column chromatography.
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.
く３−ブロモ体〉
０元素分析値
Ｃ（係）Ｈ（％’） Ｓ−Ｃ％）Ｂｒ（係）理論値
４１．４０ ３．４７ １２．２８ ３０．６０分
析値 ４０．７１ ３．３９ １）．６６ ３
１．０６０質量分析スペクトル
ＥＩ ｍ／ｅ ＝ ２６０，２６２ （Ｍつｏ
’Ｈ−ＮＭＲ（ｉ媒；ＣＤＣ１，内部標準物質；Ｔ
ＭＳ）嘗５．２５岬 ２ Ｈ−ＣＨ，−
−１，９５１）Ｐ ３ ＨＣＩＩ、 −ｏＩＲ１
７３０ｃｍ−’ エステル ν 〉Ｃ−０Ｃ−０
ｌ６２０” オレフィン ν ＞ｃ−ｃ＜１）
５０〜１）５５ ｃｍ−’ チオフェン骨格く５−
プロ上体〉
０元素分析値
Ｃ（％）Ｉ−１（％） Ｓ（係）Ｂｒ（％）理論値
４１．４０ ３．４７ １２．２８ ３０．６０分析値
４１．０１ ３．３９ １）．９０ ３０．９
４０質量分析スペクトル
ＥＩ ｍ、／ｅ ＝ ２６０． ２６２ （
Ｍ”）０ ’Ｈ−ＮＭＲ（溶媒； ＣＤＣｌ、
内部標準物質；ＴＭＳ）＝ ５．２５ ｐＰ２ Ｉ−Ｉ
−ＣＨ，−−１，９５Ｐ ３ＨＣＨ３−
ｏＩＲ１７３０ｃＩｒＬ−’ エステル ｙ ＞
ｃｍ。3-bromo body〉 0 elemental analysis value C (coupling) H (%') S-C%) Br (coupling) theoretical value
41.40 3.47 12.28 30.60 Analysis value 40.71 3.39 1). 66 3
1.060 Mass Spectrum EI m/e = 260,262 (M
'H-NMR (i medium; CDC1, internal standard substance; T
MS) 嘗5.25岬2H-CH,--1,951)P3HCII,-oIR1
730cm-' Ester ν 〉C-0C-0
l620” Olefin ν >cc<1)
50-1) 55 cm-' Thiophene skeleton 5-
Professional upper body> 0 elemental analysis value C (%) I-1 (%) S (related) Br (%) theoretical value
41.40 3.47 12.28 30.60 Analysis value 41.01 3.39 1). 90 30.9
40 Mass Spectrum EI m,/e = 260. 262 (
M'')0'H-NMR (solvent; CDCl,
Internal standard substance; TMS) = 5.25 pP2 I-I
-CH,--1,95P 3HCH3- oIR1730cIrL-' Ester y>
cm.
１６２０ ｃＷＬ−’ オレフィン ν ＞ｃｍ
ｃ＜１）５０〜１）５５０−１ チオフェン骨格1620 cWL-' Olefin ν > cm
c<1)50-1)550-1 Thiophene skeleton
第１図は本発明にがかる３、５−ジブロモ−２−メタク
リロイルオキシメチルチオフェンの気体状態での赤外線
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 3,5-dibromo-2-methacryloyloxymethylthiophene in a gaseous state according to the present invention.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21803986A JPS6377872A (en) | 1986-09-18 | 1986-09-18 | Novel brominated thiophene derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21803986A JPS6377872A (en) | 1986-09-18 | 1986-09-18 | Novel brominated thiophene derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6377872A true JPS6377872A (en) | 1988-04-08 |
Family
ID=16713685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21803986A Pending JPS6377872A (en) | 1986-09-18 | 1986-09-18 | Novel brominated thiophene derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6377872A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010000504A1 (en) * | 2008-06-30 | 2010-01-07 | Interuniversitair Microelektronica Centrum | Polymerisable compounds for making opto-electronic devices |
| WO2012058023A1 (en) | 2010-10-27 | 2012-05-03 | 3M Innovative Properties Company | Silicone resin composition having high refractive index |
-
1986
- 1986-09-18 JP JP21803986A patent/JPS6377872A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010000504A1 (en) * | 2008-06-30 | 2010-01-07 | Interuniversitair Microelektronica Centrum | Polymerisable compounds for making opto-electronic devices |
| US8450604B2 (en) | 2008-06-30 | 2013-05-28 | Imec | Polymerisable compounds for making opto-electronic devices |
| WO2012058023A1 (en) | 2010-10-27 | 2012-05-03 | 3M Innovative Properties Company | Silicone resin composition having high refractive index |
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