JP2004323450A - Method for producing aromatic ethers having phenolic hydroxyl group and alcoholic hydroxyl group - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method capable of simply producing aromatic ethers having a phenolic hydroxyl group and an alcoholic hydroxyl group in a high yield from polyhydric phenols and an oxirane compound. <P>SOLUTION: When synthesizing the aromatic ethers having the phenolic hydroxyl group and the alcoholic hydroxyl group by reacting the polyhydric phenols with the oxirane compound, the reaction is carried out by using a quaternary salt as a catalyst in the presence of a solvent having 7.0-20.0 solubility parameter to produce the aromatic ethers having the phenolic hydroxyl group and the alcoholic hydroxyl group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００２１】
で示される４級アンモニウム塩および／または４級ホスホニウム塩が好適である。なお、上記式（１）中、Ａは窒素原子またはリン原子を、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は炭化水素残基を表し、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４のうち、少なくとも１つは炭素数４以上の炭化水素残基である。また、Ｘ⁻は対イオンを表している。
【００２２】
なお、上記炭素数４以上の炭化水素残基としては、炭素数４以上の脂肪族アルキル基、脂環式アルキル基、またはアリール基が挙げられる。脂肪族アルキル基の場合は、分岐鎖を有していてもよく、脂環式アルキル基やアリール基の場合には、環上の１以上の水素が炭化水素残基で置換されていてもよい。さらに、炭素数４以上の炭化水素残基はポリマー鎖であっても構わない。Ｒ^１〜Ｒ^４は、２つ以上が炭素数４以上の炭化水素残基であることがより好ましく、３つ以上が炭素数４以上の炭化水素残基であることがさらに好ましく、４つ全てが炭素数４以上の炭化水素残基であることが特に好ましい。また、Ｒ^１〜Ｒ^４の少なくとも１つが炭素数４以上の炭化水素残基である場合、他の炭化水素残基（炭素数３以下の炭化水素残基）としては、例えば、炭素数３以下の脂肪族または脂環式アルキル基が挙げられる。この他、Ｒ^１〜Ｒ^４のいずれか２つの基が環構造（例えば、５員環や６員環など）を形成していても構わない。
【００２３】
上記Ｘ⁻に該当し得る陰イオンとしては、フッ素、塩素、臭素、ヨウ素などのハロゲン化物イオン；水酸化物イオン、有機酸のアニオン（カルボン酸アニオン、フェノキシアニオン類など）；無機酸のアニオン；などが挙げられる。無機酸のアニオンとしては、硫酸イオン、亜硫酸イオン、亜硫酸水素イオン、亜リン酸イオン、ホウ酸イオン、シアン化物イオン、炭酸イオン、チオシアン酸イオン、硝酸イオン、リン酸イオン、リン酸水素イオン、メタレートイオン（モリブデン酸イオン、タングステン酸イオン、リンタングステン酸イオン、メタバナジン酸イオン、ピロバナジン酸イオン、水素ピロバナジン酸イオン、ニオブ酸イオン、タンタル酸イオンなど）などが例示できる。これらの中でも、有機酸のアニオン、水酸化物イオン、ハロゲン化物イオンが好ましい。
【００２４】
さらに、本発明法では、出発物質である多価フェノール類およびオキシラン化合物、並びに上記触媒が溶媒に溶解または分散した状態（液体状態）で反応させて上記芳香族エーテル類を合成することが好ましい。よって、上記触媒としては、後述する溶媒に溶解し得るもの、すなわち均一系触媒が推奨される。溶媒への溶解性に着目すれば、例えば、上記一般式（１）におけるＲ^１〜Ｒ^４のうち、炭素数４以上の炭化水素残基の炭素数が、２２以下（より好ましくは１２以下）であることが望ましい。
【００２５】
これらの要求を満足し、本発明法に特に好適な４級アンモニウム塩および／または４級ホスホニウム塩の具体例としては、テトラブチルアンモニウムブロマイド、トリブチルメチルアンモニウムクロライド、トリオクチルメチルアンモニウムクロライド、トリラウリルメチルアンモニウムクロライド、ベンジルトリブチルアンモニウムクロライド、テトラオクチルアンモニウムクロライド、テトラブチルホスホニウムブロマイド、トリブチルメチルホスホニウムクロライド、トリオクチルメチルホスホニウムクロライド、トリラウリルメチルホスホニウムクロライド、ベンジルトリブチルホスホニウムクロライド、テトラオクチルホスホニウムクロライドなどが挙げられる。
【００２６】
上記触媒の使用量は特に限定されず、使用する触媒の種類や製造コストの面から適宜設定すればよいが、例えば、多価フェノール類１００質量部に対して、０．０１〜５０質量部とすることが好ましく、０．０５〜４０質量部とすることがより好ましく、０．１〜３０質量部とすることがさらに好ましい。触媒量が上記範囲を下回ると、反応の進行が遅くなる傾向にあり、経済的に好ましくない場合がある。また、触媒量が上記範囲を超えても、反応速度の向上効果が飽和する傾向にあり、やはり経済的に好ましくない。
【００２７】
本発明法で使用する溶媒は、溶解度パラメーターが７．０以上２０．０以下のものである。多価フェノール類とオキシラン化合物との反応の際に、このような溶媒を上記触媒と組み合わせて用いると、多価フェノール類の有するフェノール性水酸基の一部を残存させつつ反応を進めることが可能であり、上記芳香族エーテル類の生成の選択性が非常に高くなる。その理由は定かではないが、溶媒の溶解度パラメーターが上記範囲内の場合は、上記触媒の有する炭化水素残基［上記一般式（１）におけるＲ^１〜Ｒ^４］の溶解度パラメーターと近く、このことが反応選択性の向上に寄与しているものと考えられる。特に上記触媒において、上記一般式（１）におけるＲ^１〜Ｒ^４のうち、少なくとも１つが炭素数４以上の炭化水素残基である場合は、該炭化水素残基と溶媒の溶解度パラメーターはより近くなるため、反応選択性がさらに向上する。
【００２８】
また、溶解度パラメーターが上記範囲内にある溶媒を用いた場合には、例えば生成物（上記芳香族エーテル類）が常温で固体のものでは、反応液から該生成物を晶析により取り出す際の調整が容易となる（後述する）。
【００２９】
なお、本発明でいう「溶解度パラメーター」（δ）とは、液体間の混合性の尺度を表す指標で、正則溶液理論における凝集エネルギー密度の平方根であり、下記式（２）で表される。
【００３０】
δ＝（ΔＥ^Ｖ／Ｖ）^１／２ （２）
ここで、Ｖは溶媒のモル容積（ｃｍ^３／ｍｏｌ）を表し、ΔＥ^Ｖは２５℃における溶媒の蒸発熱（ｃａｌ／ｍｏｌ）を表す。
【００３１】
上記溶媒は、溶解度パラメーターが上記範囲内にあるものであれば特に限定されないが、例えば、ペンタン（δ＝７．０）、ヘキサン（δ＝７．３）、ヘプタン（δ＝７．４）、シクロヘキサン（δ＝８．２）、酢酸ブチル（δ＝８．５）、ｏ−キシレン（δ＝８．８）、ｐ−キシレン（δ＝８．８）、トルエン（δ＝８．９）、テトラヒドロフラン（δ＝９．１）、酢酸エチル（δ＝９．１）、ベンゼン（δ＝９．２）、メチルエチルケトン（δ＝９．３）、ジクロロメタン（δ＝９．７）、１，２−ジクロロエタン（δ＝９．８）、シクロヘキサノン（δ＝９．９）、アセトン（δ＝９．９）、１，４−ジオキサン（δ＝１０．０）、ピリジン（δ＝１０．７）、エチレングリコールモノメチルエーテル（δ＝１１．４）、１−ブタノール（δ＝１１．４）、２−プロパノール（δ＝１１．５）、アセトニトリル（δ＝１１．９）、ジメチルスルホキシド（δ＝１２．０）、ジメチルホルムアミド（δ＝１２．１）、エタノール（δ＝１２．７）、メタノール（δ＝１４．５）、エチレングリコール（δ＝１４．６）、エチレンカーボネート（δ＝１４．７）などが例示できる。このような溶媒の溶解度パラメーターは、例えば「Ａ．Ｆ．Ｍ．Ｂｕｒｔｏｎ，Ｃｈｅｍｉｃａｌ Ｒｅｖｉｅｗｓ，１９７５，Ｖｏｌ．７５，Ｎｏ．６，ｐ７３１−７５３」に開示されている。
【００３２】
本発明法では、これら例示の溶媒を１種単独で使用してもよく、２種以上を混合して用いてもよい。２種以上の溶媒を混合する場合には、混合溶媒の溶解度パラメーターが上記範囲内にあればよく、混合される各溶媒の溶解度パラメーターは特に限定されない。混合溶媒の溶解度パラメーターδ_ｍｉｘは下記式（３）により求められる。

ここで、ｎは混合する溶媒の種類を表し、ｘ，Ｖ，δは、各溶媒のモル分率、モル容積、溶解度パラメーターを表す。
【００３３】
なお、使用する溶媒の溶解度パラメーターが上記下限値を下回ると、多価フェノール類の溶解度が小さく濃度が薄くなるために上記芳香族エーテル類の生産性が低くなる。好ましい下限値は８．０、さらに好ましい下限値は８．５である。他方、溶解度パラメーターが上記上限値を超えると、上記触媒の有する炭化水素残基の溶解度パラメーターとの差が大きくなり、本発明法の効果である上記芳香族エーテル類の選択性が低下する傾向にある。好ましい上限値は１２．５、より好ましい上限値は１１．５、さらに好ましい上限値は１０．５である。上記の溶媒の中でも、例えば、酢酸ブチル（δ＝８．５）、トルエン（δ＝８．９）、メチルエチルケトン（δ＝９．３）、１，４−ジオキサン（δ＝１０．０）などが特に好ましい。
【００３４】
上記溶媒の使用量は特に限定されず、使用する溶媒の種類などに応じて適宜設定すればよいが、例えば、多価フェノール類が溶解した溶液中の多価フェノール類の濃度を１質量％９０質量％以下とすることが好ましい。多価フェノール類濃度が上記下限値を下回ると、反応の進行が遅くなり生産性が低下する傾向にある。より好ましい下限値は５質量％、さらに好ましい下限値は１０質量％である。他方、上記上限値を超えると、副反応が生じ易くなり、上記芳香族エーテル類の選択性が低下する傾向にある。より好ましい上限値は８０質量％、さらに好ましい上限値は７０質量％、特に好ましい上限値は６０質量％である。
【００３５】
また、本発明法における上記反応の形態は特に限定されず、例えば上記反応をバッチ方式で実施してもよく、連続方式で実施しても構わない。連続方式の場合は触媒を反応釜内に懸濁させることもでき、触媒を固定床として反応原料を通過させることで反応を進行させることもできる。また、本発明法では、原料は反応中に均一に混合していることが好ましいが、反応できる状態にある限り２層に分離していても構わない。
【００３６】
上記芳香族エーテル類を合成する際の、多価フェノール類とオキシラン化合物との組成比は特に制限されないが、多価フェノール類が有するフェノール性水酸基のうち、オキシラン化合物を付加させるフェノール性水酸基１モルに対し、オキシラン化合物を０．１モル以上２モル以下とすることが一般的である。上記下限値を下回ると、反応の進行が遅くなり、上記芳香族エーテル類の生産性が低下する傾向にある。より好ましい下限値は０．５モルであり、さらに好ましい下限値は０．８モルである。他方、上記上限値を超えると、副反応が生じ易くなり、上記芳香族エーテルの選択性が低下する傾向にある。より好ましい上限値は１．５モルであり、さらに好ましい上限値は１．２モルである。
【００３７】
多価フェノール類とオキシラン化合物とを反応させる際の温度は特に限定されず、使用する触媒の種類などに応じて適宜設定すればよいが、例えば、０℃以上１８０℃以下とすることが一般的である。温度が上記下限値を下回ると、反応の進行が遅くなり生産性が低下する傾向にある。より好ましい温度の下限値は２０℃、さらに好ましい下限値は４０℃である。他方、温度が上記上限値を超えると、副反応が生じ易くなり、上記芳香族エーテル類の選択性が低下する傾向にある。より好ましい上限値は１５０℃、さらに好ましい上限値は１２０℃、特に好ましい上限値は１００℃である。
【００３８】
反応の際の圧力は特に限定されず、使用するオキシラン化合物の種類などに応じて適宜設定すればよい。例えば、オキシラン化合物としてエチレンオキサイドを使用する場合には、不活性ガスで加圧することが、エチレンオキサイドの溶媒への溶解度を大きくし、反応効率を高め得るために好ましい。また、圧力の上限については、反応装置のコスト面から制約される。
【００３９】
上記反応を実施する系内の雰囲気は、使用するオキシラン化合物の種類などに応じて適宜設定すればよい。通常、オキシラン化合物には爆発の危険性があるため、不活性ガス雰囲気（例えば、窒素雰囲気）とすることが好ましい。また、多価フェノール類は酸素の存在によりキノン類に酸化され易いため、かかる面からも不活性ガス雰囲気とすることが推奨される。
【００４０】
なお、上記芳香族エーテル類の合成の際には、多価フェノール類の全量とオキシラン化合物の全量を混合して反応させることも可能であるが、該反応は発熱反応であるため、多価フェノール類にオキシラン化合物を逐次投入する方法を採用することが好ましい。したがって、本発明法を実施する反応装置は、反応温度や反応圧力を上記好適範囲内に設定可能であり、さらに反応系内を不活性ガス雰囲気にし得ると共に、オキシラン化合物を逐次投入することができる装置を採用することが望ましい。なお、オキシラン化合物を逐次投入する場合の投入速度は特に限定されず、使用する装置の除熱能力などに応じた速度とすればよい。
【００４１】
また、多価フェノール類とオキシラン化合物との好適な反応時間は、上述の各反応条件に応じて変動するが、例えば、１〜２４時間とすることが一般的であり、１〜１２時間とすることが、生産性の観点からより好ましい。
【００４２】
上記反応を終了して得られる反応液は、用途に応じてそのまま使用してもよく、必要に応じて溶媒を除去した混合物（未反応物や副生物を含む）として、あるいは精製により上記芳香族エーテル類を取り出して使用することも可能である。精製方法は特に限定されず、公知の各種精製方法の中から、使用した触媒などに応じて適宜選択すればよい。例えば、蒸留による方法、晶析による方法、カラムを用いる方法などが採用できる。
【００４３】
例えば、上記芳香族エーテル類が常温で固体の場合には、本発明法で用いる溶媒中において、反応終了後の加温状態では溶液状態であり、該溶液を冷却すれば結晶が析出するように、反応時または反応直後の溶媒量（溶液濃度）を調整することが容易であり、これにより精製が簡易且つ良好に達成できる。この場合の各種条件は、使用する溶媒の種類に応じて適宜決定すればよい。
【００４４】
生成した上記芳香族エーテル類は、上記の反応液や混合物、あるいは精製して目的化合物（芳香族エーテル類）の純度を高めた状態で、希釈剤、安定剤などを加えて保存や輸送を行うことができる。
【００４５】
本発明法によって製造される芳香族エーテル類［好ましくはフェノール性水酸基を有するフェニルヒドロキシアルキルエーテル類、より好ましくは、ｏ−ヒドロキシアルコキシフェノール類］は、分子内にフェノール性水酸基とアルコール性水酸基を有するため、これらの官能基に基づく特性を利用して、様々な用途に適用し得る。例えば、高沸点溶媒（常温で液体のもの）、各種化学品の原料などの用途がある。
【００４６】
また、フェノール性水酸基の殺菌作用を利用して、香粧品分野や医薬品分野での用途もあり、例えば、安全性の高い皮膚外用剤として有用である。さらに、集積回路作成用レジスト組成物としての用途もあり、かかる組成物は、良好な解像度、焦点深度、現像性を有し、且つ感度、レジストパターン断面形状および保存安定性に優れるものとなる。さらに自動車の防食用のプライマーコーティングなどに使用されるカチオン性電着塗装組成物への用途もある。この場合、カチオン電着塗装組成物に用いられるポリイソシアネートのキャップ剤として利用される。
【００４７】
【実施例】
以下、実施例に基づいて本発明を詳細に述べる。ただし、下記実施例は本発明を制限するものではなく、前・後記の趣旨を逸脱しない範囲で変更実施をすることは、全て本発明の技術的範囲に包含される。なお、本実施例で用いる「％」は、特に断らない限り質量基準である。
【００４８】
実施例１
下記手順に従い、カテコールのモノ（ヒドロキシプロピル）エーテル［ｏ−ヒドロキシプロポキシフェノール］の合成を行った。５０ｍｌガラス製耐圧容器に、カテコール：５．００ｇ、プロピレンオキサイド：３．１６ｇ、溶媒としてトルエン（δ＝８．９）：１０．０ｇ、および触媒としてテトラメチルアンモニウムクロライド：８８ｍｇを仕込んだ後、気相部を窒素置換し密閉した。このガラス製耐圧容器を１００℃のオイルバスに入れ、振とうしながら４時間反応を行った。こうして得られた反応液をガスクロマトグラフィーで分析し、下記に定義するカテコール転化率、モノ（ヒドロキシプロピル）エーテル（モノ体）およびビス（ヒドロキシプロピル）エーテル（ビス体）選択率、並びにモノ体収率を求めた。

結果を表１に示す。
【００４９】
実施例２、３
触媒を、テトラブチルアンモニウムブロマイド：２５８ｍｇ（実施例２）、あるいはテトラオクチルアンモニウムブロマイド：４３７ｍｇ（実施例３）に変更した以外は、実施例１と同様にしてカテコールのモノ（ヒドロキシプロピル）エーテル［ｏ−ヒドロキシプロポキシフェノール］）の合成を行い、実施例１と同様にして生成物（反応液）の分析を行った。結果を表１に示す。
【００５０】
実施例４〜６
触媒をテトラオクチルアンモニウムブロマイド：４３７ｍｇとし、溶媒を、酢酸ブチル（δ＝８．５）（実施例４）、エチレングリコールモノメチルエーテル（δ＝１１．４）（実施例５）、あるいはジメチルホルムアミド（δ＝１２．１）（実施例６）に変更した以外は、実施例１と同様にしてカテコールのモノ（ヒドロキシプロピル）エーテル［ｏ−ヒドロキシプロポキシフェノール］の合成を行い、実施例１と同様にして生成物（反応液）の分析を行った。結果を表１に示す。
【００５１】
比較例
触媒をテトラオクチルアンモニウムブロマイド：４３７ｍｇとし、溶媒を水（δ＝２３．４）に変更した他は、実施例１と同様にしてカテコールのモノ（ヒドロキシプロピル）エーテル［ｏ−ヒドロキシプロポキシフェノール］の合成を行い、実施例１と同様にして生成物（反応液）の分析を行った。結果を表１に示す。
【００５２】
【表１】

【００５３】
表１において、「Ｍｅ_４ＮＣｌ」はテトラメチルアンモニウムクロライドを、「Ｂｕ_４ＮＢｒ」はテトラブチルアンモニウムブロマイドを、「Ｏｃ_４ＮＢｒ」はテトラオクチルアンモニウムブロマイドを、「ＥＧＭＭＥ」はエチレングリコールモノメチルエーテルを、「ＤＭＦ」はジメチルホルムアミドを、「δ」は溶解度パラメーターを、「モノ体」はカテコールのモノ（ヒドロキシプロピル）エーテルを、「ビス体」はカテコールのビス（ヒドロキシプロピル）エーテルを、夫々意味している。
【００５４】
表１から分かるように、適切な溶媒を採用して合成を行った実施例１〜６では、カテコール転化率が良好であり、目的とするカテコールのモノ（ヒドロキシプロピル）エーテルの収率も高い。
【００５５】
これに対し、比較例は不適切な溶媒を採用して合成を行った例である。すなわち、溶解度パラメーターの値が大きな溶媒である水（δ＝２３．４）を用いた場合には、カテコール転化率が非常に低く、また、目的とするカテコールのモノ（ヒドロキシプロピル）エーテルの収率も極端に低い。
【００５６】
【発明の効果】
本発明は以上のように構成されており、多価フェノール類とオキシラン化合物を反応させるに当たり、特定の触媒と溶媒を組み合わせて使用することで、多価フェノール類が有していたフェノール性水酸基の一部を残存させて、フェノール性水酸基およびアルコール性水酸基を有する芳香族エーテル類を高い収率で合成し得る製造方法が提供できる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing an aromatic ether having a corresponding phenolic hydroxyl group and alcoholic hydroxyl group from a polyhydric phenol and an oxirane compound.
[0002]
[Prior art]
Aromatic ethers having a phenolic hydroxyl group and an alcoholic hydroxyl group, such as o-hydroxyalkoxyphenols, have been applied to many fields by utilizing the properties of the phenolic hydroxyl group and the alcoholic hydroxyl group in the molecule. Various synthetic methods have been proposed for synthesizing such aromatic ethers.
[0003]
For example, Patent Literature 1 discloses a method of synthesizing phenylhydroxyalkyl ether by reacting a dihydric phenol such as catechol, resorcinol, or hydroquinone with an alkylene oxide such as ethylene oxide in an alkaline environment.
[0004]
Patent Document 2 discloses that an oxirane compound is added to hydroquinone, which is a polyhydric phenol, in the presence of a catalyst selected from the group consisting of a quaternary ammonium halide compound, a quaternary ammonium phosphonium compound, and a quaternary ammonium hydroxide compound. A method for reacting ethylene oxide is disclosed.
[0005]
However, according to the methods disclosed in Patent Literature 1 and Patent Literature 2, most of the dihydric phenol (dihydroxybenzene) is converted into a bis (hydroxyalkyl) ether, and even when the reaction product is purified, the mono (hydroxyalkyl) There was a problem that the yield of the ether compound was low.
[0006]
[Patent Document 1]
JP-B-51-4977
[Patent Document 2]
Japanese Patent Publication No. 54-1291
[0007]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, and an object thereof is to easily produce aromatic ethers having a phenolic hydroxyl group and an alcoholic hydroxyl group from a polyhydric phenol and an oxirane compound in a high yield. The purpose is to provide a way to gain.
[0008]
[Means for Solving the Problems]
The production method of the present invention, which has achieved the above object, comprises reacting a polyhydric phenol with an oxirane compound to form an aromatic ether having a phenolic hydroxyl group and an alcoholic hydroxyl group (hereinafter, simply referred to as "aromatic ethers"). In synthesizing the compound of the present invention, the gist lies in that the above reaction is carried out using a quaternary salt as a catalyst in the presence of a solvent having a solubility parameter of 7.0 to 20.0. The catalyst is preferably a quaternary salt having a hydrocarbon residue having 4 or more carbon atoms.
[0009]
Examples of the aromatic ethers having a phenolic hydroxyl group and an alcoholic hydroxyl group include, for example, phenylhydroxyalkyl ethers having a phenolic hydroxyl group, and more specifically, o-hydroxyalkoxyphenols [mono (hydroxy of catechols) Alkyl ether)]. That is, the production method of the present invention is suitable for producing such a compound.
[0010]
As the polyhydric phenols, for example, dihydric phenols such as catechol, resorcinol, and hydroquinone are preferable, and as the oxirane compound, an aliphatic alkylene oxide, more specifically, ethylene oxide or propylene oxide is preferably used. Is done.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
When reacting a polyhydric phenol with an oxirane compound to synthesize aromatic ethers, the present inventors require that a simple apparatus leave at least one phenolic hydroxyl group of the polyhydric phenol as a starting material. As a result of intensive studies aimed at increasing the yield of the product (aromatic ethers) and the product (aromatic ethers), when the synthesis was carried out by combining a specific catalyst and a solvent, the purpose was achieved at a high level. And completed the present invention. Hereinafter, the characteristic that allows at least one of the phenolic hydroxyl groups to remain and that can synthesize the target product of the present invention in high yield may be referred to as “selectivity (reaction selectivity)”.
[0012]
The raw materials (polyhydric phenols and oxirane compounds) used in the method of the present invention may be either solid or liquid, and there is no particular limitation on the form and purity.
[0013]
The polyhydric phenols refer to aromatic compounds containing two or more phenolic hydroxyl groups in the molecule. The aromatic compound is a compound having an aromatic ring, and the aromatic ring includes a non-benzene-based aromatic ring such as a cyclopentadiene ring; a benzene ring; a condensed aromatic ring such as a naphthalene ring, an anthracene ring and a pyrene ring; Heteroaromatic ring (pyrrole ring, pyridine ring, thiophene ring, furan ring) in which at least one carbon atom of a system aromatic ring, aromatic ring or condensed aromatic ring is replaced by a heteroatom such as oxygen atom, nitrogen atom, sulfur atom, etc. Etc.);
[0014]
Specific examples of the above polyhydric phenols include catechols (catechol, protocatechuic acid, chloracetylpyrocatechin, adrenaline, adrenaline, apomorphine, urushiol, tiron, phenylfluorone, etc.), resorcinols (resorcinol, orcin, hexylresorcinol) Dihydric phenols such as hydroquinones (2,3,5-trimethylhydroquinone, 2-t-butylhydroquinone, homogentisate, etc.); pyrogallols (pyrogallol, 2,3,4-trihydroxybenzophenone, gallic acid) Trivalent phenols such as lauryl, gallic acid ester, purprogalin, etc., phloroglucins (phloroglucin, etc.), oxyhydroquinones (oxyhydroquinone, etc.); bis (3,5- Methyl-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2,2′-methylenebis (4-ethyl-6-t -Butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (4-methyl-6-t-butylphenol), 3,9-bis (1,1- Dimethyl-2 (β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) ethyl-2,4,8,10-tetraoxaspiro (5,5) undecane, aluminone, atlanoline, erythrin , Catechin, epicatechin, isocartamine, curcumin, coclaurine, cyanidin, syringidine, stilbestrol, tan Bisphenols such as acid esters, bisphenol A, phenol red, phlorizin, hexestrol, hematoxylin, pelargonidin, morin, recanolic acid; 1,4-dihydroxynaphthalene, carbonyl J acid, (R) -1,1′-biphenol Hydroxynaphthalenes such as -2-naphthol, (S) -1,1'-bi-2-naphthol, eriochrome black T, α-binaphthol, β-binaphthol, γ-binaphthol; 1,4-dihydroxyanthraquinone, leuco -1,4-diaminoanthraquinone, leuco-1,4-dihydroxyanthraquinone, anthrahydroquinone, alizarin, alizarin S, emodin, quinizarin, kermesate, acidic anthraquinone dyes (such as alizarin safilol B), purpurin, and purp Hydroxyanthracenes or hydroxyanthraquinones such as xanthine; citrazic acid; 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane; 1,3,5-trimethyl-2,4 , 6-tris (3,5-di-t-hydroxybenzyl) benzene; atromentin; anthraquinone dye (condensed purple); usnic acid; dehydrourushiol; echinochrome; orseric acid ester; cartamine; , Chrom fast nebble B, palatin fast blue, etc.); dihydrophenylalanine ester; dilophoric acid ester; desphinidin; vitamin P; sulfolecein; polyporic acid; Lumpur like; and the like.
[0015]
Among the above polyhydric phenols, dihydric phenols such as catechols, resorcinols, and hydroquinones are recommended. For example, catechols are preferable, and catechol is particularly preferable.
[0016]
The oxirane compound means a compound having one or more epoxy rings (three-membered ethers) in the molecule. Specific examples of the oxirane compound include aliphatic alkylene oxides such as ethylene oxide, propylene oxide, isobutylene oxide, 2,3-butylene oxide, and pentylene oxide; aromatic alkylene oxides such as styrene oxide; cyclohexene oxide; epichlorohydrin; No. These oxirane compounds may be used alone or in combination of two or more. Among the above oxirane compounds, aliphatic alkylene oxides are preferable, and ethylene oxide or propylene oxide is particularly preferable.
[0017]
The catalyst used in the method of the present invention is a quaternary salt such as a quaternary ammonium salt and / or a quaternary phosphonium salt. When the above aromatic ethers are synthesized from polyhydric phenols and oxirane compounds using these catalysts, the reaction can be advanced in high yield.
[0018]
The catalyst is not particularly limited as long as it is a quaternary ammonium salt and / or a quaternary phosphonium salt. Specifically, tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetraoctylammonium chloride, tetraoctylammonium bromide, tetraoctylammonium iodide, tributylmethylammonium chloride, trioctylmethylammonium Chloride, trilaurylmethylammonium chloride, benzyltributylammonium chloride, phenyltrimethylammonium chloride, strong basic ion exchange resin [for example, DIAION PA306, PA406, TSA-1200 (all manufactured by Mitsubishi Chemical Corporation); Dowex MSA-1, Dowex SAR (both from Dow Chemical); Ambera Quaternary ammonium salts such as tetramethylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetraoctylphosphonium And quaternary phosphonium salts such as chloride, tetraoctylphosphonium bromide, tetramethylphosphonium iodide, tributylmethylphosphonium chloride, trioctylmethylphosphonium chloride, trilaurylmethylphosphonium chloride, and benzyltributylphosphonium chloride.
[0019]
For example, among the above quaternary ammonium salts and / or quaternary phosphonium salts, those having a hydrocarbon residue having 4 or more carbon atoms are preferable, and more preferable are those having the following general formula ( 1)
[0020]
Embedded image

[0021]
The quaternary ammonium salt and / or quaternary phosphonium salt represented by In the above formula (1), A represents a nitrogen atom or a phosphorus atom; ¹ , R ² , R ³ , R ⁴ Represents a hydrocarbon residue; ¹ , R ² , R ³ , R ⁴ At least one of them is a hydrocarbon residue having 4 or more carbon atoms. Also, X ⁻ Represents a counter ion.
[0022]
The hydrocarbon residue having 4 or more carbon atoms includes an aliphatic alkyl group having 4 or more carbon atoms, an alicyclic alkyl group, and an aryl group. In the case of an aliphatic alkyl group, it may have a branched chain, and in the case of an alicyclic alkyl group or an aryl group, one or more hydrogen atoms on the ring may be substituted with a hydrocarbon residue. . Further, the hydrocarbon residue having 4 or more carbon atoms may be a polymer chain. R ¹ ~ R ⁴ Is more preferably two or more hydrocarbon residues having 4 or more carbon atoms, still more preferably three or more hydrocarbon residues having four or more carbon atoms, and all four are preferably four or more carbon atoms. Is particularly preferred. Also, R ¹ ~ R ⁴ Is a hydrocarbon residue having 4 or more carbon atoms, the other hydrocarbon residue (hydrocarbon residue having 3 or less carbon atoms) is, for example, an aliphatic or alicyclic having 3 or less carbon atoms. And an alkyl group. In addition, R ¹ ~ R ⁴ May form a ring structure (for example, a 5-membered ring or a 6-membered ring).
[0023]
X above ⁻ Examples of the anion which may be applicable include halide ions such as fluorine, chlorine, bromine and iodine; hydroxide ions, anions of organic acids (such as carboxylate anions and phenoxy anions); and anions of inorganic acids. Can be Examples of inorganic acid anions include sulfate, sulfite, hydrogen sulfite, phosphite, borate, cyanide, carbonate, thiocyanate, nitrate, phosphate, hydrogen phosphate, and metaphosphate. Rate ions (molybdate ion, tungstate ion, phosphotungstate ion, metavanadate ion, pyrovanadate ion, hydrogen pyrovanadate ion, niobate ion, tantalate ion, etc.) can be exemplified. Among these, anions, hydroxide ions and halide ions of organic acids are preferred.
[0024]
Furthermore, in the method of the present invention, it is preferable to synthesize the aromatic ethers by reacting the starting materials, that is, the polyhydric phenol and the oxirane compound, and the catalyst in a state of being dissolved or dispersed in a solvent (liquid state). Therefore, as the above-mentioned catalyst, a catalyst which can be dissolved in a solvent described later, that is, a homogeneous catalyst is recommended. Focusing on the solubility in a solvent, for example, R in the general formula (1) ¹ ~ R ⁴ Among them, the hydrocarbon residue having 4 or more carbon atoms preferably has 22 or less (more preferably 12 or less) carbon atoms.
[0025]
Specific examples of the quaternary ammonium salt and / or quaternary phosphonium salt satisfying these requirements and particularly suitable for the method of the present invention include tetrabutylammonium bromide, tributylmethylammonium chloride, trioctylmethylammonium chloride, trilaurylmethyl. Examples include ammonium chloride, benzyltributylammonium chloride, tetraoctylammonium chloride, tetrabutylphosphonium bromide, tributylmethylphosphonium chloride, trioctylmethylphosphonium chloride, trilaurylmethylphosphonium chloride, benzyltributylphosphonium chloride, and tetraoctylphosphonium chloride.
[0026]
The amount of the catalyst used is not particularly limited, and may be appropriately set in view of the type of the catalyst to be used and the production cost. For example, the amount is 0.01 to 50 parts by mass with respect to 100 parts by mass of the polyhydric phenol. The amount is preferably 0.05 to 40 parts by mass, more preferably 0.1 to 30 parts by mass. If the amount of the catalyst is below the above range, the progress of the reaction tends to be slow, which may be economically undesirable. Further, even if the amount of the catalyst exceeds the above range, the effect of improving the reaction rate tends to be saturated, which is also not economically preferable.
[0027]
The solvent used in the method of the present invention has a solubility parameter of 7.0 or more and 20.0 or less. When such a solvent is used in combination with the above catalyst during the reaction between the polyhydric phenol and the oxirane compound, it is possible to proceed with the reaction while leaving a part of the phenolic hydroxyl group of the polyhydric phenol. In addition, the selectivity of the generation of the aromatic ethers becomes very high. Although the reason is not clear, when the solubility parameter of the solvent is within the above range, the hydrocarbon residue of the catalyst [R in the general formula (1)] ¹ ~ R ⁴ ], Which is thought to contribute to the improvement of the reaction selectivity. In particular, in the above catalyst, R in the above general formula (1) ¹ ~ R ⁴ When at least one of them is a hydrocarbon residue having 4 or more carbon atoms, the solubility parameter of the hydrocarbon residue and the solvent becomes closer, so that the reaction selectivity is further improved.
[0028]
When a solvent having a solubility parameter within the above range is used, for example, when the product (the aromatic ethers) is a solid at room temperature, adjustment when removing the product from the reaction solution by crystallization is performed. (Described later).
[0029]
The “solubility parameter” (δ) in the present invention is an index indicating a measure of the miscibility between liquids, is the square root of the cohesive energy density in regular solution theory, and is represented by the following equation (2).
[0030]
δ = (ΔE ^V / V) ^1/2 (2)
Where V is the molar volume of the solvent (cm ³ / Mol) and ΔE ^V Represents the evaporation heat (cal / mol) of the solvent at 25 ° C.
[0031]
The solvent is not particularly limited as long as the solubility parameter is within the above range. For example, pentane (δ = 7.0), hexane (δ = 7.3), heptane (δ = 7.4), Cyclohexane (δ = 8.2), butyl acetate (δ = 8.5), o-xylene (δ = 8.8), p-xylene (δ = 8.8), toluene (δ = 8.9), Tetrahydrofuran (δ = 9.1), ethyl acetate (δ = 9.1), benzene (δ = 9.2), methyl ethyl ketone (δ = 9.3), dichloromethane (δ = 9.7), 1,2- Dichloroethane (δ = 9.8), cyclohexanone (δ = 9.9), acetone (δ = 9.9), 1,4-dioxane (δ = 10.0), pyridine (δ = 10.7), ethylene Glycol monomethyl ether (δ = 11.4), 1-butanol (δ = 111. 4), 2-propanol (δ = 11.5), acetonitrile (δ = 11.9), dimethyl sulfoxide (δ = 12.0), dimethylformamide (δ = 12.1), ethanol (δ = 12.7) ), Methanol (δ = 14.5), ethylene glycol (δ = 14.6), ethylene carbonate (δ = 14.7) and the like. The solubility parameter of such a solvent is disclosed, for example, in "AFM Burton, Chemical Reviews, 1975, Vol. 75, No. 6, p731-753".
[0032]
In the method of the present invention, one of these exemplified solvents may be used alone, or two or more of them may be used in combination. When two or more solvents are mixed, the solubility parameter of the mixed solvent only needs to be within the above range, and the solubility parameter of each mixed solvent is not particularly limited. Mixed solvent solubility parameter δ _mix Is determined by the following equation (3).

Here, n represents the type of solvent to be mixed, and x, V, and δ represent the mole fraction, molar volume, and solubility parameter of each solvent.
[0033]
If the solubility parameter of the solvent used is below the above lower limit, the solubility of the polyhydric phenols is low and the concentration is low, so that the productivity of the aromatic ethers is low. A preferred lower limit is 8.0, and a more preferred lower limit is 8.5. On the other hand, when the solubility parameter exceeds the above upper limit, the difference between the solubility parameter of the hydrocarbon residue having the catalyst becomes large, and the selectivity of the aromatic ethers, which is an effect of the method of the present invention, tends to decrease. is there. A preferred upper limit is 12.5, a more preferred upper limit is 11.5, and a still more preferred upper limit is 10.5. Among the above solvents, for example, butyl acetate (δ = 8.5), toluene (δ = 8.9), methyl ethyl ketone (δ = 9.3), 1,4-dioxane (δ = 10.0) and the like. Particularly preferred.
[0034]
The amount of the solvent used is not particularly limited, and may be appropriately set according to the type of the solvent used. For example, the concentration of the polyhydric phenol in the solution in which the polyhydric phenol is dissolved is 1% by mass 90%. It is preferable that the content be not more than mass%. When the concentration of the polyhydric phenols is lower than the above lower limit, the progress of the reaction tends to be slow and the productivity tends to decrease. A more preferred lower limit is 5% by mass, and a still more preferred lower limit is 10% by mass. On the other hand, if it exceeds the upper limit, side reactions tend to occur, and the selectivity of the aromatic ethers tends to decrease. A more preferred upper limit is 80% by mass, a still more preferred upper limit is 70% by mass, and a particularly preferred upper limit is 60% by mass.
[0035]
The form of the reaction in the method of the present invention is not particularly limited. For example, the reaction may be performed in a batch system or a continuous system. In the case of a continuous system, the catalyst can be suspended in the reaction vessel, and the reaction can be advanced by passing the reaction raw material as a fixed bed using the catalyst. Further, in the method of the present invention, the raw materials are preferably mixed uniformly during the reaction, but may be separated into two layers as long as they can be reacted.
[0036]
When synthesizing the aromatic ethers, the composition ratio of the polyhydric phenol and the oxirane compound is not particularly limited. Among the phenolic hydroxyl groups of the polyhydric phenol, 1 mol of a phenolic hydroxyl group to which the oxirane compound is added is added. In general, the amount of the oxirane compound is 0.1 mol or more and 2 mol or less. If the ratio is below the lower limit, the progress of the reaction tends to be slow, and the productivity of the aromatic ethers tends to decrease. A more preferred lower limit is 0.5 mol, and a still more preferred lower limit is 0.8 mol. On the other hand, if it exceeds the upper limit, side reactions tend to occur, and the selectivity of the aromatic ether tends to decrease. A more preferred upper limit is 1.5 mol, and a still more preferred upper limit is 1.2 mol.
[0037]
The temperature at which the polyhydric phenol is reacted with the oxirane compound is not particularly limited, and may be appropriately set according to the type of the catalyst to be used. It is. When the temperature is lower than the above lower limit, the progress of the reaction tends to be slow, and the productivity tends to decrease. A more preferred lower limit of the temperature is 20 ° C, and a still more preferred lower limit is 40 ° C. On the other hand, when the temperature exceeds the upper limit, side reactions tend to occur, and the selectivity of the aromatic ethers tends to decrease. A more preferred upper limit is 150 ° C, a still more preferred upper limit is 120 ° C, and a particularly preferred upper limit is 100 ° C.
[0038]
The pressure at the time of the reaction is not particularly limited, and may be appropriately set according to the type of the oxirane compound used and the like. For example, when ethylene oxide is used as the oxirane compound, pressurization with an inert gas is preferable in order to increase the solubility of ethylene oxide in the solvent and increase the reaction efficiency. Further, the upper limit of the pressure is restricted from the viewpoint of the cost of the reactor.
[0039]
The atmosphere in the system in which the above reaction is carried out may be appropriately set according to the type of the oxirane compound used and the like. Usually, since the oxirane compound has a risk of explosion, it is preferable to use an inert gas atmosphere (for example, a nitrogen atmosphere). In addition, since polyhydric phenols are easily oxidized to quinones due to the presence of oxygen, it is recommended to use an inert gas atmosphere from this aspect.
[0040]
In the synthesis of the aromatic ethers, it is possible to mix and react the entire amount of the polyhydric phenol and the entire amount of the oxirane compound. However, since the reaction is an exothermic reaction, It is preferable to adopt a method of sequentially charging the oxirane compound to the product. Therefore, in the reactor for carrying out the method of the present invention, the reaction temperature and the reaction pressure can be set within the above preferred ranges, the reaction system can be set to an inert gas atmosphere, and the oxirane compound can be sequentially charged. It is desirable to employ a device. In addition, the charging speed when the oxirane compound is sequentially charged is not particularly limited, and may be a speed according to the heat removal capability of the device to be used.
[0041]
The suitable reaction time between the polyhydric phenol and the oxirane compound varies depending on the above-described reaction conditions, but is generally, for example, 1 to 24 hours, and is 1 to 12 hours. Is more preferable from the viewpoint of productivity.
[0042]
The reaction solution obtained after completion of the above reaction may be used as it is depending on the intended use, or may be used as a mixture from which the solvent has been removed (including unreacted substances and by-products) as necessary, or the above-mentioned aromatic compound may be purified. It is also possible to take out the ethers and use them. The purification method is not particularly limited, and may be appropriately selected from various known purification methods according to the used catalyst and the like. For example, a method by distillation, a method by crystallization, a method using a column, and the like can be adopted.
[0043]
For example, when the aromatic ethers are solid at room temperature, the solvent used in the method of the present invention is in a solution state in a heated state after the completion of the reaction, and the solution is cooled so that crystals are precipitated. In addition, it is easy to adjust the amount of the solvent (solution concentration) during or immediately after the reaction, whereby the purification can be easily and satisfactorily achieved. Various conditions in this case may be appropriately determined according to the type of the solvent used.
[0044]
The aromatic ethers thus produced are stored or transported by adding a diluent, a stabilizer or the like in the above-mentioned reaction solution or mixture, or in a state where the purity of the target compound (aromatic ethers) is increased by purification. be able to.
[0045]
Aromatic ethers [preferably phenylhydroxyalkyl ethers having a phenolic hydroxyl group, more preferably o-hydroxyalkoxyphenols] produced by the method of the present invention have a phenolic hydroxyl group and an alcoholic hydroxyl group in the molecule. Therefore, it can be applied to various uses by utilizing the characteristics based on these functional groups. For example, there are uses such as high boiling point solvents (liquid at room temperature) and raw materials for various chemicals.
[0046]
Further, utilizing the bactericidal action of the phenolic hydroxyl group, it is also used in the cosmetics and pharmaceutical fields, and is useful, for example, as a highly safe skin external preparation. Further, the composition is used as a resist composition for producing an integrated circuit. Such a composition has good resolution, depth of focus, and developability, and is excellent in sensitivity, resist pattern cross-sectional shape, and storage stability. Further, there is also a use for a cationic electrodeposition coating composition used for a primer coating for corrosion protection of automobiles and the like. In this case, it is used as a capping agent for the polyisocyanate used in the cationic electrodeposition coating composition.
[0047]
【Example】
Hereinafter, the present invention will be described in detail based on examples. However, the following embodiments do not limit the present invention, and all modifications and alterations without departing from the spirit of the preceding and following embodiments are included in the technical scope of the present invention. Note that “%” used in this example is based on mass unless otherwise specified.
[0048]
Example 1
Catechol mono (hydroxypropyl) ether [o-hydroxypropoxyphenol] was synthesized according to the following procedure. After charging 5.00 g of catechol, 3.16 g of propylene oxide, 10.0 g of toluene (δ = 8.9) as a solvent, and 88 mg of tetramethylammonium chloride as a catalyst in a 50 ml glass pressure vessel, the air was charged. The phase was replaced with nitrogen and sealed. This glass pressure vessel was placed in an oil bath at 100 ° C., and the reaction was carried out for 4 hours while shaking. The reaction solution thus obtained was analyzed by gas chromatography, and the conversion of catechol, the selectivity of mono (hydroxypropyl) ether (mono-form) and bis (hydroxypropyl) ether (bis-form), and the yield of mono-form as defined below were determined. The rate was determined.

Table 1 shows the results.
[0049]
Examples 2 and 3
Catechol mono (hydroxypropyl) ether [o] was obtained in the same manner as in Example 1 except that the catalyst was changed to 258 mg of tetrabutylammonium bromide (Example 2) or 437 mg of tetraoctylammonium bromide (Example 3). -Hydroxypropoxyphenol]), and the product (reaction liquid) was analyzed in the same manner as in Example 1. Table 1 shows the results.
[0050]
Examples 4 to 6
The catalyst was tetraoctyl ammonium bromide: 437 mg, and the solvent was butyl acetate (δ = 8.5) (Example 4), ethylene glycol monomethyl ether (δ = 11.4) (Example 5), or dimethylformamide (δ). = 12.1) Except for changing to (Example 6), synthesis of catechol mono (hydroxypropyl) ether [o-hydroxypropoxyphenol] was performed in the same manner as in Example 1, and the same as in Example 1. The product (reaction liquid) was analyzed. Table 1 shows the results.
[0051]
Comparative example
Synthesis of catechol mono (hydroxypropyl) ether [o-hydroxypropoxyphenol] in the same manner as in Example 1 except that the catalyst was tetraoctyl ammonium bromide: 437 mg and the solvent was changed to water (δ = 23.4). The product (reaction liquid) was analyzed in the same manner as in Example 1. Table 1 shows the results.
[0052]
[Table 1]

[0053]
In Table 1, "Me ₄ NCl ”is tetramethylammonium chloride,“ Bu ₄ “NBr” is tetrabutylammonium bromide, “Oc ₄ “NBr” is tetraoctyl ammonium bromide, “EGMME” is ethylene glycol monomethyl ether, “DMF” is dimethylformamide, “δ” is solubility parameter, “mono form” is catechol mono (hydroxypropyl) ether, "Bis form" means the bis (hydroxypropyl) ether of catechol, respectively.
[0054]
As can be seen from Table 1, in Examples 1 to 6 in which synthesis was performed using an appropriate solvent, the conversion rate of catechol was good, and the yield of mono (hydroxypropyl) ether of the target catechol was high.
[0055]
On the other hand, the comparative example is an example in which synthesis was performed using an inappropriate solvent. That is, when water (δ = 23.4), which is a solvent having a large solubility parameter value, is used, the conversion of catechol is very low, and the yield of mono (hydroxypropyl) ether of the target catechol is low. Is also extremely low.
[0056]
【The invention's effect】
The present invention is configured as described above, when reacting a polyhydric phenol and an oxirane compound, by using a specific catalyst and a solvent in combination, the phenolic hydroxyl group of the polyhydric phenol has It is possible to provide a production method capable of synthesizing aromatic ethers having a phenolic hydroxyl group and an alcoholic hydroxyl group at a high yield while leaving a part thereof.

Claims (3)

In reacting polyhydric phenols with oxirane compounds to synthesize aromatic ethers having phenolic hydroxyl groups and alcoholic hydroxyl groups,
In the presence of a solvent having a solubility parameter of 7.0 to 20.0,
A process for producing aromatic ethers having a phenolic hydroxyl group and an alcoholic hydroxyl group, wherein the reaction is carried out using a quaternary salt as a catalyst. The method according to claim 1, wherein the catalyst is a quaternary salt having a hydrocarbon residue having 4 or more carbon atoms. 3. The method according to claim 1, wherein the polyhydric phenol is a dihydric phenol.