JP2002275171A - Oxetane ring-containing broomphenyl derivative - Google Patents
Oxetane ring-containing broomphenyl derivativeInfo
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- JP2002275171A JP2002275171A JP2001084100A JP2001084100A JP2002275171A JP 2002275171 A JP2002275171 A JP 2002275171A JP 2001084100 A JP2001084100 A JP 2001084100A JP 2001084100 A JP2001084100 A JP 2001084100A JP 2002275171 A JP2002275171 A JP 2002275171A
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- oxetane ring
- derivative
- reaction
- oxetane
- alkali metal
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、カチオン重合が可
能であるオキセタン環を有する新規なブロモフェニル誘
導体およびその製造方法に関するものである。TECHNICAL FIELD The present invention relates to a novel bromophenyl derivative having an oxetane ring capable of cationic polymerization and a method for producing the same.
【０００２】[0002]
【従来の技術】オキセタン化合物は、光カチオン重合ま
たは光カチオン硬化が可能なモノマーとして、近年注目
を浴びている化合物であり、これまでに多くの単官能性
および多官能性オキセタン化合物が報告されている。例
えば、Pure Appl. Chem.,A29(10), pp. 915(1992) およ
びPure Appl.Chem.,A30(2&3),pp.189 (1993)には種
々のオキセタン誘導体の合成法が記載されている。ま
た、特開平６−１６８０４号公報には、下記式（２）で
表されるオキセタン化合物が開示されている。2. Description of the Related Art Oxetane compounds are attracting attention in recent years as monomers capable of photocationic polymerization or photocationic curing, and many monofunctional and polyfunctional oxetane compounds have been reported so far. I have. For example, Pure Appl.Chem., A29 (10), pp. 915 (1992) and Pure Appl.Chem., A30 (2 & 3), pp. 189 (1993) describe methods for synthesizing various oxetane derivatives. Have been. Further, Japanese Patent Application Laid-Open No. Hei 6-16804 discloses an oxetane compound represented by the following formula (2).
【０００３】[0003]
【化２】 Embedded image
【０００４】（式中、Ｒ1は水素原子、炭素数1〜6のア
ルキル基、フルオロアルキル基、アリル基、アリール
基、フリル基またはチエニル基、フッ素原子を示し、Ｒ
2は、鎖状または分岐状ポリ（アルキレンオキシ）基、
キシリレン基、シロキサン結合およびエステル結合から
成る群から選ばれる多価基を示し、Ｚは酸素原子または
硫黄原子を示し、ｍは２、３または４である。）(Wherein R 1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group, an allyl group, an aryl group, a furyl group or a thienyl group, a fluorine atom;
2 is a chain or branched poly (alkyleneoxy) group,
A polyvalent group selected from the group consisting of a xylylene group, a siloxane bond and an ester bond, Z represents an oxygen atom or a sulfur atom, and m is 2, 3 or 4. )
【０００５】また、ＤＥ１，０２１，８５８には、下記
式（３）で表されるオキセタン化合物が開示されてい
る。[0005] DE 1,021,858 discloses an oxetane compound represented by the following formula (3).
【０００６】[0006]
【化３】 Embedded image
【０００７】（式中、Ｒは２以上の原子価を有する芳香
族残基を示し、Ｒ1は水素原子、アルキル基またはアリ
ール基を示し、ｎは１または２である）(Wherein, R represents an aromatic residue having a valence of 2 or more, R 1 represents a hydrogen atom, an alkyl group or an aryl group, and n is 1 or 2)
【０００８】また、特開平７−１７９５８号公報にはア
リルクロライドとヒドロキシメチルオキセタンとの反応
によるオキセタン化合物の合成法が記載されている。Japanese Patent Application Laid-Open No. 7-17958 describes a method for synthesizing an oxetane compound by reacting allyl chloride with hydroxymethyloxetane.
【０００９】さらに、特開平８−２４５７８３号公報に
は、ナフタレン骨格を有する二官能性オキセタンを始め
とする数多くのオキセタン化合物類の記載がある。ま
た、特開平８−２４５７８３号公報には、オキセタン環
を有するフェニル誘導体が記載されている。しかしなが
ら、これらいずれの公知文献にも本発明におけるブロモ
フェニル誘導体についての記載は全くなく、また合成法
についても具体的な例は全く記載されていない。本発明
のオキセタン環を有するブロモフェニル誘導体はフェニ
ル誘導体に比べ、臭素を含有するため、臭素が置換され
ていないフェニル誘導体と比べて、高い屈折率と優れた
難燃性を有するものと期待される。Further, Japanese Patent Application Laid-Open No. Hei 8-245783 describes a large number of oxetane compounds including a bifunctional oxetane having a naphthalene skeleton. Further, Japanese Patent Application Laid-Open No. Hei 8-245783 describes a phenyl derivative having an oxetane ring. However, none of these publicly known documents describes the bromophenyl derivative in the present invention, and no specific example is described about the synthesis method. Since the bromophenyl derivative having an oxetane ring of the present invention contains bromine as compared with a phenyl derivative, it is expected to have a high refractive index and excellent flame retardancy as compared with a phenyl derivative in which bromine is not substituted. .
【００１０】[0010]
【本発明が解決しようとする課題】本発明は、容易に入
手可能な原料から合成できる、オキセタン環を有するブ
ロモフェニル誘導体およびそれらの製造方法を提供する
ものである。SUMMARY OF THE INVENTION The present invention provides a bromophenyl derivative having an oxetane ring, which can be synthesized from readily available raw materials, and a process for producing the same.
【００１１】[0011]
【課題を解決するための手段】本発明は、下記式（１）
で表されるオキセタン環を有するブロモフェニル誘導体
であり、および第２発明は水酸化アルカリ金属、アルカ
リ金属水素化物またはアルカリ金属の存在下、ブロモフ
ェノールと３−アルキル−３−クロロメチルオキセタン
または３−クロロメチルオキセタンとを反応させること
を特徴とする前記オキセタン環を有するブロモフェニル
誘導体の製造方法である。Means for Solving the Problems The present invention provides the following formula (1)
And a second invention is a bromophenyl derivative having an oxetane ring represented by the formula: and bromophenol and 3-alkyl-3-chloromethyloxetane or 3-bromo-3-oxane in the presence of an alkali metal hydroxide, an alkali metal hydride or an alkali metal. A method for producing a bromophenyl derivative having an oxetane ring, which comprises reacting bromomethyloxetane with chloromethyloxetane.
【００１２】[0012]
【化４】 Embedded image
【００１３】（式中、Ｒ1は水素原子または１〜４個の
炭素原子を有するアルキル基を示し、ｎは１〜５の整数
である。）Wherein R 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 5.
【００１４】[0014]
【発明の実施の形態】本発明のオキセタン環を有するブ
ロモフェニル誘導体は、例えば、水酸化アルカリ金属、
アルカリ金属水素化物またはアルカリ金属の存在下に、
ブロモフェノールと３−アルキル−３−クロロメチルオ
キセタンまたは３−クロロメチルオキセタンとを反応さ
せて製造することができる。なお、この反応において必
要であれば反応溶媒として芳香族炭化水素溶媒を用いる
ことができ、さらに反応をより効率的に行なうために相
関移動触媒を用いることができる。BEST MODE FOR CARRYING OUT THE INVENTION The bromophenyl derivative having an oxetane ring of the present invention is, for example, an alkali metal hydroxide,
In the presence of alkali metal hydride or alkali metal,
It can be produced by reacting bromophenol with 3-alkyl-3-chloromethyloxetane or 3-chloromethyloxetane. In this reaction, if necessary, an aromatic hydrocarbon solvent can be used as a reaction solvent, and a phase transfer catalyst can be used for more efficiently performing the reaction.
【００１５】水酸化アルカリ金属としては、５〜６０質
量％の水溶液状あるいは粉末状にした水酸化ナトリウム
および水酸化カリウム等が挙げられ、これらの中でも好
ましくは４０〜５０質量％の水溶液状のものである。ア
ルカリ金属水素化物としては、水素化ナトリウムおよび
水素化カリウム等が挙げられ、さらに、アルカリ金属と
しては、金属ナトリウムおよび金属カリウム等が挙げら
れる。これらのアルカリ金属類の使用割合は、ブロモフ
ェノールのフェノール性水酸基に対して、アルカリのモ
ル比で１〜４倍量であることが好ましく、さらに好まし
くは１〜２倍量である。Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide in the form of an aqueous solution of 5 to 60% by mass or in the form of powder. Among them, those in the form of an aqueous solution of 40 to 50% by mass are preferred. It is. Examples of the alkali metal hydride include sodium hydride and potassium hydride, and examples of the alkali metal include sodium metal and potassium potassium. The use ratio of these alkali metals is preferably 1 to 4 times, more preferably 1 to 2 times the molar ratio of alkali to the phenolic hydroxyl group of bromophenol.
【００１６】反応溶媒として用いることができる芳香族
炭化水素溶媒としては、ベンゼン、トルエンおよびキシ
レン等が好適に用いられる。As the aromatic hydrocarbon solvent which can be used as the reaction solvent, benzene, toluene, xylene and the like are preferably used.
【００１７】また、相間移動触媒としては、公知の相間
移動触媒（例えば、Ｗ．Ｐ．Ｗｅｂｅｒ，Ｇ．Ｗ．Ｇｏ
ｋｅｌ共著、田伏岩夫、西谷孝子共訳「相間移動触
媒」、(株)化学同人発行などに記載のもの）のいずれも
用いることができるが、これらの中でも、触媒としての
能力の高さから、有機第４級アンモニウム塩およびホス
ホニウム塩が好ましい。具体例としては、テトラ−ｎ−
ブチルアンモニウムブロミド、ベンジルトリエチルアン
モニウムブロミド、トリオクチルメチルアンモニウムク
ロリド、テトラ−ｎ−ブチルホスホニウムクロリド、ト
リオクチルエチルホスホニウムブロミドおよびテトラフ
ェニルホスホニウムクロリドなどが挙げられる。As the phase transfer catalyst, known phase transfer catalysts (for example, WP Weber, GW Go)
Kel, co-authored by Iwio Tabushi, Takako Nishitani, “Phase Transfer Catalyst”, and those described in Kagaku Doujin Co., Ltd.), among which, because of their high ability as a catalyst, Organic quaternary ammonium salts and phosphonium salts are preferred. As a specific example, tetra-n-
Butylammonium bromide, benzyltriethylammonium bromide, trioctylmethylammonium chloride, tetra-n-butylphosphonium chloride, trioctylethylphosphonium bromide, tetraphenylphosphonium chloride and the like.
【００１８】前記ブロモフェノールと３−アルキル−３
−クロロメチルオキセタンまたは３−クロロメチルオキ
セタンとの反応における反応温度は８０〜１５０℃であ
ることが好ましく、特に１００〜１２０℃であることが
好ましい。反応時間は、反応温度や相関移動触媒の使用
の有無にもよるが、４〜５０時間であることが好まし
い。The above bromophenol and 3-alkyl-3
The reaction temperature in the reaction with -chloromethyloxetane or 3-chloromethyloxetane is preferably from 80 to 150 ° C, particularly preferably from 100 to 120 ° C. The reaction time depends on the reaction temperature and whether or not a phase transfer catalyst is used, but is preferably 4 to 50 hours.
【００１９】上記反応終了後は、室温まで冷却した反応
液を、水洗および蒸留をすることにより、前記式（１）
で表される目的とするオキセタン環を有するブロモフェ
ニル誘導体を得ることができる。この化合物の構造は1
Ｈ−ＮＭＲおよび13Ｃ−ＮＭＲ によって確認できる。
前記式（１）中のＲ1は、水素原子または1〜４個の炭素
原子を有するアルキル基を示すが、特にメチル基またエ
チル基が好ましい。After the completion of the above reaction, the reaction solution cooled to room temperature is washed with water and distilled to obtain the above-mentioned formula (1).
A bromophenyl derivative having an intended oxetane ring represented by the following formula can be obtained. The structure of this compound is 1
It can be confirmed by 1 H-NMR and 13 C-NMR.
R 1 in the formula (1) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is particularly preferably a methyl group or an ethyl group.
【００２０】[0020]
【実施例】以下に実施例を用いて、本発明を具体的に説
明するが、本発明はこれら実施例に限定されるものでは
ない。 実施例1 温度計、コンデンサー、攪拌装置、滴下漏斗兼窒素ガス
吹込口を備えた１Ｌの四つ口丸底フラスコに、２，４，
６−トリブロモフェノールを２６４．６ｇ（０．８ｍｏ
ｌ）と３−クロロメチル−３−エチルオキセタン３２
３．１ｇ（２．４ｍｏｌ）を入れ攪拌しながら、４８質
量％の水酸化カリウム水溶液１３６．７ｇ（ＫＯＨとし
て１．１７ｍｏｌ）を滴下漏斗から２０分間かけて滴下
した。ここに触媒としてテトラブチルアンモニウムブロ
ミド１０．３ｇを添加した後、還流するまで(約１１０
℃）昇温し、還流下で６時間反応を続けた。反応終了
後、室温まで冷却した反応液を分液ロートに移し、純水
を３３０ｇ、塩化メチレンを７００ｇ添加してよく攪拌
した。有機相と水相を分離した後、有機相を５００ｍｌ
の純水で５回洗浄した。その後、洗浄した有機相を減圧
蒸留することにより、３−エチル−３−（２，４，６−
トリブロモフェノキシメチル）オキセタンを得た。ＧＣ
分析の結果、得られた化合物の純度は９９．３％であ
り、反応後の収率は３８％であった。1Ｈ−ＮＭＲおよ
び13Ｃ−ＮＭＲ（１Ｈ照射)の結果より得られた化合物
は下記式（４）で表される、３−エチル−３−（２，
４，６−トリブロモフェノキシメチル）オキセタンであ
ると同定された。EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. Example 1 Into a 1 L four-necked round bottom flask equipped with a thermometer, a condenser, a stirrer, a dropping funnel and a nitrogen gas inlet, 2, 4,
264.6 g of 6-tribromophenol (0.8 mol
l) and 3-chloromethyl-3-ethyloxetane 32
While stirring 3.1 g (2.4 mol), 136.7 g (1.17 mol as KOH) of a 48 mass% aqueous potassium hydroxide solution was added dropwise from a dropping funnel over 20 minutes while stirring. After adding 10.3 g of tetrabutylammonium bromide as a catalyst, the mixture is refluxed (about 110 g).
° C), and the reaction was continued under reflux for 6 hours. After the completion of the reaction, the reaction solution cooled to room temperature was transferred to a separating funnel, and 330 g of pure water and 700 g of methylene chloride were added, followed by sufficient stirring. After separating the organic and aqueous phases, the organic phase is
Was washed 5 times with pure water. Thereafter, the washed organic phase was distilled under reduced pressure to give 3-ethyl-3- (2,4,6-
Tribromophenoxymethyl) oxetane was obtained. GC
As a result of analysis, the purity of the obtained compound was 99.3%, and the yield after the reaction was 38%. The compound obtained from the results of 1 H-NMR and 13 C-NMR (irradiation with 1 H) was 3-ethyl-3- (2,
4,6-tribromophenoxymethyl) oxetane.
【００２１】[0021]
【化５】 Embedded image
【００２２】1Ｈ−ＮＭＲ(重アセトン溶媒)の測定結
果：δ(ppm) J(Hz)； a;1.04(t J=7.5Hz)、b;1.95(q J
=7.5Hz)、c;4.19(s) 、d;4.56(d J=82Hz d J=5.9Hz)、
h;7.85(s)13 Ｃ−ＮＭＲ(重アセトン溶媒、1H照射)の測定結果：δ
(ppm)；a;8.57、b;27.14、c;75.73、d;77.51、e;44.5
3、f;153.09、g;119.70、h;136.10、ｉ;118.28Measurement results of 1 H-NMR (deuterated acetone solvent): δ (ppm) J (Hz); a; 1.04 (t J = 7.5 Hz), b; 1.95 (q J
= 7.5Hz), c; 4.19 (s), d; 4.56 (d J = 82Hz d J = 5.9Hz),
h; 7.85 (s) 13 C-NMR (deuterated acetone solvent, 1H irradiation): δ
(ppm); a; 8.57, b; 27.14, c; 75.73, d; 77.51, e; 44.5
3, f; 153.09, g; 119.70, h; 136.10, i; 118.28
【００２３】実施例２ 攪拌機、温度計、脱水管およびコンデンサーを取り付け
たガラス製の２Ｌの四つ口丸底フラスコに、２，４，６
−トリブロモフェノールを６６１．６ｇ（２ｍｏｌ）、
８５質量％の顆粒状の水酸化カリウムを１３８．６ｇ
（ＫＯＨとして２．１ｍｏｌ）、３−クロロメチル−３
−エチルオキセタン６７３．０ｇ（５ｍｏｌ）を入れ攪
拌しながら、１２０℃に昇温した。反応液の温度を約１
２０℃に保ちながら、反応系中の圧力が約２００ｍｍHg
になるようにし、反応系中の水を３−クロロメチル−３
−エチルオキセタンと共沸させ、水を留去しながら４４
時間反応させた。なお、脱水管中の有機相はすべて反応
器へ戻した。反応終了までに留出した水は５２．６ｇで
あった。反応終了後、室温まで冷却した反応液を分液ロ
ートに移し、純水を９００ｇ、塩化メチレンを３，００
０ｇ添加してよく攪拌した。有機相と水相を分離した
後、有機相を５００ｍｌの純水で3回洗浄した。その
後、有機相を減圧蒸留することにより、３−エチル−３
−（２，４，６−トリブロモフェノキシメチル）オキセ
タンを得た。ＧＣ分析の結果、得られた化合物の純度は
９９．６％であり、反応後の収率は３４％であった。1
Ｈ−ＮＭＲおよび13Ｃ−ＮＭＲ（１Ｈ照射）の結果より
得られた化合物は前記式（４）で表される、３−エチル
−３−（２，４，６−トリブロモフェノキシメチル）オ
キセタンであり実施例１と同じ化合物であった。Example 2 A glass 2L four-necked round bottom flask equipped with a stirrer, a thermometer, a dehydrating tube and a condenser was charged with 2, 4, 6
661.6 g (2 mol) of tribromophenol,
138.6 g of 85% by mass of granular potassium hydroxide
(2.1 mol as KOH), 3-chloromethyl-3
673.0 g (5 mol) of -ethyloxetane was added, and the temperature was raised to 120 ° C while stirring. When the temperature of the reaction solution is about 1
While maintaining at 20 ° C, the pressure in the reaction system is about 200mmHg
And the water in the reaction system is 3-chloromethyl-3
Azeotrope with ethyl oxetane and remove water
Allowed to react for hours. All organic phases in the dehydration tube were returned to the reactor. The amount of water distilled by the end of the reaction was 52.6 g. After completion of the reaction, the reaction solution cooled to room temperature was transferred to a separating funnel, and 900 g of pure water and 3,000 methylene chloride were added.
0 g was added and stirred well. After separating the organic phase and the aqueous phase, the organic phase was washed three times with 500 ml of pure water. Thereafter, the organic phase was distilled under reduced pressure to obtain 3-ethyl-3.
-(2,4,6-Tribromophenoxymethyl) oxetane was obtained. As a result of GC analysis, the purity of the obtained compound was 99.6%, and the yield after the reaction was 34%. 1
The compound obtained from the results of 1 H-NMR and 13 C-NMR (irradiation with 1 H) was 3-ethyl-3- (2,4,6-tribromophenoxymethyl) oxetane represented by the formula (4). Yes, the same compound as in Example 1.
【００２４】[0024]
【発明の効果】本発明のオキセタン環を有するブロモフ
ェニル誘導体から誘導される光硬化性又は熱硬化性樹脂
は高屈折率であり、硬化性、耐熱性および機械特性に優
れるため、塗料・コーティング材、接着剤およびレンズ
等に利用できる。The photocurable or thermosetting resin derived from the bromophenyl derivative having an oxetane ring of the present invention has a high refractive index and is excellent in curability, heat resistance and mechanical properties. , Adhesives and lenses.
Claims (2)
するブロモフェニル誘導体。 【化１】 （式中、Ｒ1は水素原子または１〜４個の炭素原子を有
するアルキル基を示し、ｎは１〜５の整数である。）1. A bromophenyl derivative having an oxetane ring represented by the following formula (1). Embedded image (In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 5.)
物またはアルカリ金属の存在下、ブロモフェノールと３
−アルキル−３−クロロメチルオキセタンまたは３−ク
ロロメチルオキセタンとを反応させることを特徴とする
請求項１記載のオキセタン環を有するブロモフェニル誘
導体の製造方法。2. A method according to claim 1, wherein said bromophenol is reacted with bromophenol in the presence of an alkali metal hydroxide, an alkali metal hydride or an alkali metal.
2. The method for producing a bromophenyl derivative having an oxetane ring according to claim 1, wherein the reaction is carried out with -alkyl-3-chloromethyloxetane or 3-chloromethyloxetane.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007111098A1 (en) | 2006-03-24 | 2007-10-04 | Konica Minolta Medical & Graphic, Inc. | Transparent barrier sheet and method for producing same |
| WO2007111074A1 (en) | 2006-03-24 | 2007-10-04 | Konica Minolta Medical & Graphic, Inc. | Transparent barrier sheet and method for producing transparent barrier sheet |
| WO2007111092A1 (en) | 2006-03-24 | 2007-10-04 | Konica Minolta Medical & Graphic, Inc. | Transparent barrier sheet and method for producing transparent barrier sheet |
| WO2007111075A1 (en) | 2006-03-24 | 2007-10-04 | Konica Minolta Medical & Graphic, Inc. | Transparent barrier sheet and method for producing transparent barrier sheet |
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- 2001-03-23 JP JP2001084100A patent/JP4023097B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007111098A1 (en) | 2006-03-24 | 2007-10-04 | Konica Minolta Medical & Graphic, Inc. | Transparent barrier sheet and method for producing same |
| WO2007111074A1 (en) | 2006-03-24 | 2007-10-04 | Konica Minolta Medical & Graphic, Inc. | Transparent barrier sheet and method for producing transparent barrier sheet |
| WO2007111092A1 (en) | 2006-03-24 | 2007-10-04 | Konica Minolta Medical & Graphic, Inc. | Transparent barrier sheet and method for producing transparent barrier sheet |
| WO2007111075A1 (en) | 2006-03-24 | 2007-10-04 | Konica Minolta Medical & Graphic, Inc. | Transparent barrier sheet and method for producing transparent barrier sheet |
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