JP4080896B2 - Compounds useful as novel low molecular organic gelation or solidification agents, and gelation or solidification agents and gelation or solidification products containing the compounds as active ingredients - Google Patents

Description

【０００９】
【化４】

【００１０】
前記一般式１および２においてＸ、ＹおよびＺは、Ｈ、Ｃ_ｍＨ_２ｍ＋１、ＯＣ_ｎＨ_２ｎ＋１、ＳＣ _ｑ Ｈ _２ｑ＋１ からそれぞれ独立に選択される。ｍ、ｎおよびｑは１〜２０の整数であり、各ｍ、ｎおよびｑは独立に選択される。
【００１１】
本発明の第２は、前記一般式１で表されるＮ，Ｎ’−ジベンゾイル尿素誘導体または前記一般式２の化合物を含む新規なゲル化剤または固化剤と少なくとも１種の動植物油脂、エステル、アルコール、炭化水素系油剤、徐放性の香料、徐放性の植物精油、揮散性消臭剤および揮散性抗菌性薬剤からなる群から選択される被ゲル化または被固化成分とを含むゲル化または固化した製品である。好ましくは、少なくとも１種の被ゲル化または被固化成分がα−ピネン、β−ピネン、リモネン、リナロール、ゲラニオール、シトラール、スクワレン、カレン、α−ファルネセン、β−ファルネセン、α−グアイエン、ｄ−グアイエン、α−カリオフィレン、β−カリオフィレン、ｄ−カジネン、γ−カジネン、α−ビザボレン、γ−ビザボレン、α−セドレン、β−セドレン、バレンセン、ツヨプセン、ターピネン、ネロール、シトロネロール、ファルネソール、ネロリドール、α−ビザボロール、β−カリオフィレンアルコール、α−サンタロール、β−サンタロール、ベチベロール、セドロール、エチルヘキサノエート、シス−３−ヘキセノール、アルコールＣ−６、リナリルアセテート、ネリルアセテート、シトラール、シトロネラール、ターピネオールおよびメチルヨノンからなる群から選択される香料であることを特徴とする前記のゲル化または固化した製品、（２）ジャスミン油、ローズ油、テレピン油、オレンジ油、ベルガモット油、イランイラン油、ハナマス油、ラベンダー油、ゼラニウム油、シトロネラ油、セージ油、ペパーミント油、スペアミント油、レモン油、レモングラス油、ローズマリー油、バジル油、クローブ油、コリアンダー油、ユーカリ油、ゼラニウム油、ジンジャー油、グレープフルーツ油、ヒバ油、ヒノキ油、ラバンジン油、タイム油、ライムオイル、シナモンリーフ油、ハッカハク油、アニス油、プチグレン油、ローレル油、パイン油、ハッカ油およびツェーデル油からなる群から選択される植物精油であることを特徴とする前記のゲル化または固化した製品または（３）ピルビン酸エステル、ヒノキチオールおよびアリルチオイソシアネートからなる群から選択される揮散性剤であることを特徴とする前記のゲル化または固化した製品である。
【００１２】
【本発明の実施の態様】
本発明をより詳細に説明する。
I．前記本発明の一般式１で表されるＮ，Ｎ’−ジベンゾイル尿素誘導体は、尿素と２当モル量以上のクロロ安息香酸類を原料とし、適当なアルカリ触媒、例えば４−ジメチルアミノピリジン（ＤＭＡＰ）を用いて、反応媒体、例えばピリジン中で反応させることによりアミド化合物とすることができる。この反応は０℃ないし１００℃で１時間ないし１２時間反応させることによって行うことができる。
アルカリ触媒としては、前記ＤＭＡＰ以外に水素化ナトリウム、トリエチルアミン、１，５−ジアビシクロ〔４．３．０〕ノナ−５−エン、１，８−ジアビシクロ〔５．４．０〕ウンデカ−７−エン、炭酸カリウム、炭酸ナトリウムを例示できる。また、反応媒体としては前記ピリジン以外にジエチルエーテル、テトラヒドロフラン、ジオキサンなどのエーテル類、ベンゼン、トルエン、キシレンなどの芳香族炭化水素類、ヘキサメチレンリン酸トリアミド、ジメチルスルホキシド、Ｎ−メチルピペリジン、Ｎ-メチルピロリジン、ピコリンを例示できる。
前記反応行程において、反応物中に未反応の原料や副生成物が残存する場合には減圧蒸留、溶媒分別などの公知の手段で精製することができる。例えば、反応物の精製は、減圧下での未反応物質の除去、酢酸エチルやヘキサンなどの有機溶媒による再結晶、活性白土、活性炭、シリカゲル、アルミナなどの吸着処理、その他により行うことができ、必要に応じてこれらを単独でもしくは組み合わせて適用すればよい。
一般式２の化合物は尿素を
下記の化合物Ｗに代えることにより同様に合成できる。
【００１３】
【化５】

【００１４】
II．本発明前記一般式１の新規化合物は、香料、医薬品、化粧品、塗料、インク、潤滑油、農業、水産および各種電池の電解質や、繊維、樹脂、高分子、ゴム、金属等の加工分野を含む産業において利用される各種有機液体のゲル化または固化剤として有用である。
前記有機液体としては、胡麻油、大豆油、菜種油、コーン油、サフラワー油、ヒマワリ油、綿実油、オリーブ油、パーム油、ヒマシ油、魚油、豚油、牛脂等の動植物油脂類、ミスチリン酸イソプロピル、トリ−２−エチルヘキサン酸グリセリド、ミスチリン酸２−オクチルドデシル等のエステル類、メタノール、エタノール、デカノールなどのアルコール類、灯油、軽油、重油、流動パラフィン、イソパラフィン等の炭化水素系油剤、またヘキサン、ドデカンなどの有機溶剤や廃食用油、廃潤滑油、廃金属加工油剤等の回収または再利用の廃油類を対象とすることができる。
【００１５】
この他、前記一般式１の新規化合物は、香料、植物精油、揮散性消臭剤、抗菌性薬剤などをゲル化もしくは固化した薬剤徐放性製剤の製造にも有用である。
前記香料は単体香料ならびに調合香料でもかまわない。具体的には、α−ピネン、β−ピネン、リモネン、リナロール、ゲラニオール、シトラール、スクワレン、カレン、α−ファルネセン、β−ファルネセン、α−グアイエン、ｄ−グアイエン、α−カリオフィレン、β−カリオフィレン、ｄ−カジネン、γ−カジネン、α−ビザボレン、β-ビザボレン、γ−ビザボレン、α−セドレン、β−セドレン、バレンセン、ツヨプセン、ターピネン、ネロール、シトロネロール、ファルネソール、ネロリドール、α−ビザボロール、β−カリオフィレンアルコール、α−サンタロール、β−サンタロール、ベチベロール、セドロール、エチルヘキサノエート、シス−３−ヘキセノール、アルコールＣ−６、リナリルアセテート、ネリルアセテート、シトロネラール、ターピネオール、メチルヨノンなどを挙げることができる。
【００１６】
前記植物精油では、ジャスミン油、ローズ油、テレピン油、オレンジ油、ベルガモット油、イランイラン油、ハナマス油、ラベンダー油、ゼラニウム油、シトロネラ油、セージ油、ペパーミント油、スペアミント油、レモン油、レモングラス油、ローズマリー油、バジル油、クローブ油、コリアンダー油、ユーカリ油、ゼラニウム油、ジンジャー油、グレープフルーツ油、ヒバ油、ヒノキ油、ラバンジン油、タイム油、ライムオイル、シナモンリーフ油、ハッカハク油、アニス油、プチグレン油、ローレル油、パイン油、ハッカ油、ツェーデル油などを挙げることができる。
【００１７】
前記揮散性消臭剤としては、特開平６−１２１８２２記載のピルビン酸エチル、ピルビン酸フェニルエチルなどのピルビン酸エステルを、そして前記抗菌性薬剤としては、ヒノキチオール、アリルチオイソシアネートなどを挙げることができる。
【００１８】
III．本発明のゲル化または固化剤の使用法は、前記有機液体、香料、植物精油、揮散性消臭剤または抗菌性薬剤１ｍＬに対し、本発明のゲル化または固化剤を、Ｎ，Ｎ’−ジベンゾイル尿素誘導体として０．１〜５０ｍｇ、好ましくは０．３〜２０ｍｇ添加し、所望により６０〜１２０℃程度に加熱して均一状態になるまで攪拌した後、常温にて静置すれば、ゲル化物または固化物を調整することができる。
また、本発明のゲル化または固化剤は単独でも使用できるが、公知のゲル化剤、天然ワックスまたは合成ワックス等の固化剤等、本発明のゲル化または固化剤の特性を減じない範囲で併用してもよい。
【００１９】
【実施例】
以下、実施例により本発明を具体的に説明するが、この例示により本発明が限定的に解釈されるものではない。
実施例１
下記のスキーム１による、Ｎ，Ｎ’−ジ（３，４，５−トリドデシルオキシベンゾイル）尿素（化合物Ｂ）の合成；
【００２０】
【化６】

【００２１】
３，４，５−トリドデシルオキシ安息香酸（８１０ｍｇ，１．２ｍｍｏｌ）に、塩化チオニル３ｍＬを加え３時間加熱還流後、塩化チオニルを留去して，塩化３，４，５−トリドデシルオキシベンゾイル（Ａ）を得た。尿素(３０ｍｇ，０．５ｍｍｏｌ)と４−ジメチルアミノピリジン(ＤＭＡＰ，１２．２ｍｇ，０．１ｍｍｏｌ)をピリジン５ｍＬに溶かし、これに塩化３，４，５−トリドデシルオキシベンゾイル（Ａ）を加え、室温下６時間攪拌した。その後、飽和硫酸水素カリウム水溶液を加えクロロホルムで抽出（３回）し、硫酸ナトリウムで乾燥した。溶媒を留去し、残渣をシリカゲルカラムクロマトグラフィー（展開溶媒 クロロホルム）により分離精製し、Ｎ，Ｎ’−ジ（３，４，５−トリドデシルオキシベンゾイル）尿素（Ｂ）を得た。（収率５８４ｍｇ，８５％）
【００２２】
（Ｂ）の物性；
^１Ｈ−ＮＭＲ（４００ ＭＨｚ，ＣＤＣｌ_３）
０．８８（１８Ｈ，ｔ，Ｊ＝７．０ Ｈｚ）
１．２６−１．５２（１０８Ｈ，ｍ）
１．７５（４Ｈ，ｑｕｉｎ，Ｊ＝６．６ Ｈｚ）
１．８４（８Ｈ，ｑｕｉｎ，Ｊ＝６．６ Ｈｚ）
４．０５（４Ｈ，ｔ，Ｊ＝６．６ Ｈｚ）
４．０６（８Ｈ，ｔ，Ｊ＝６．６ Ｈｚ）
７．１４（４Ｈ、ｓ）
ＦＡＢ ＭＳ（マススペクトル ７０ｅＶ） ｍ／ｚ １３７４（Ｍ＋Ｈ）
元素分析値（測定値）Ｃ，７５．９３；Ｈ， １１．３８；Ｎ，１．９９％
（理論値）Ｃ_８７Ｈ_１５６Ｎ_２Ｏ_９：Ｃ，７６．０４；Ｈ， １１．４４；Ｎ，２．０４％
【００２３】
実施例２
実施例１で得られた、Ｎ，Ｎ’−ジ（３，４，５−トリドデシルオキシベンゾイル）尿素（Ｂ）を、濃度が２重量％となるように、表１に記載の各有機溶媒に添加し、これを試験管に入れ、約７０℃に加熱後、常温（２５℃）にて静置冷却したときの状態を観察し、このときの内容物の流動性の有無、また流動性のないものについてはゲル化物の固さを、ゲル調製後、逆さに試験管を立てて、１時間後、ゲルの重さに耐えられ、そのままの状態のものを硬いものと評価した。評価は４段階評価、すなわち、◎：流動性なし、ゲル化物は均一で固い、○：流動性なし、ゲル化物は均一で軟らかい、△：流動性ややあり、×：不均一混合物または均一だが流動性あり、を行った。実験結果を以下の表−１に示す。
【００２４】
【表１】

【００２５】
実施例３
実施例１で得られたＮ，Ｎ’−ジ（３，４，５−トリドデシルオキシベンゾイル）尿素（Ｂ）を、濃度が０．５重量％となるよう各種香料および植物精油を添加した試験管に入れ、約８０℃ないし１００℃に加熱後、常温（２５℃）にて静置冷却したときの状態を観察し、このときの内容物の流動性の有無、また流動性のないものについてはゲル化物の固さを調べた。実施例２と同様に４段階評価、すなわち、◎：流動性なし、ゲル化物は均一で固い、○：流動性なし、ゲル化物は均一で軟らかい、△：流動性ややあり、×：不均一混合物または均一だが流動性あり、を行った。さらに、ゲル化物の香気の有無を２段階評価、すなわち、◎：香気あり、×：香気なし、を行った。実験結果を表−２に示す。
【００２６】
【表２】

【００２７】
前記両結果から、Ｎ，Ｎ’−ジ（３，４，５−トリドデシルオキシベンゾイル）尿素（Ｂ）は前記種々の有機液体に対して効果的なゲル化剤であり、芳香成分に対しても好ましいゲル化剤であることを示している。また、前記香料および植物製油に対して均一で滑らかなゲル化合物が形成されることが明らかになった。
【００２８】
実施例４；徐放性の固化した製品としての有用性を示す。
実施例１で得られたＮ，Ｎ’−ジ（３，４，５−トリドデシルオキシベンゾイル）尿素（Ｂ）を、濃度が０．３重量％となるようラベンダー油を添加した試験管に入れ、約８０℃ないし１００℃に加熱後、室温にて静置冷却したときの時間の経過（０，７，１５，３７日）に伴うゲル化物の重量変化を調べた。また、時間の経過の経過に伴うゲル化物の状態を観察し、このときの内容物の流動性の有無、また流動性のないものについてはゲル化物の固さを調べた。実施例２と同様に４段階評価、すなわち、◎：流動性なし、ゲル化物は均一で固い、○：流動性なし、ゲル化物は均一で軟らかい、△：流動性ややあり、×：不均一混合物または均一だが流動性あり、を行った。さらに、ゲル化物の香気の有無を２段階評価、すなわち、◎：香気あり、×：香気なし、を行った。また、比較として、ラベンダー油の時間の経過（０，７，１５，３７日）に伴う重量変化を調べた。実験結果を表−３に示す。
【００２９】
【表３】

【００３０】
実施例５
一般式２に属する下記の式Ｃの化合物のスキーム２による合成；
【００３１】
【化７】

【００３２】
【化８】

【００３３】
３，４，５―トリドデシルオキシ安息香酸（８１０ mg， １．２ mmol）に、塩化チオニル３mlを加え３時間加熱還流後、塩化チオニルを留去して，塩化３，４，５―トリドデシルオキシベンゾイル（化合物Ａ）を得た。２，２‘―ジアミノ―５，５’―ビトロポン(１２０ mg， ０．５ mmol)と４―ジメチルアミノピリジン(ＤＭＡＰ， １２．２ mg， ０．１ mmol) をピリジン ５ ｍｌに溶かし、これに塩化３，４，５―トリドデシルオキシベンゾイルを加え、室温下６時間攪拌した。その後、飽和硫酸水素カリウム水溶液を加えクロロホルムで抽出（３回）し、硫酸ナトリウムで乾燥した。溶媒を留去し、残渣をシリカゲルカラムクロマトグラフィー（展開溶媒 クロロホルム）により分離精製し、２，２‘―ビス（３，４，５―トリドデシルオキシベンゾイルアミノ）―５，５’―ビトロポン（Ｃ）を得た。（収率５８３ ｍｇ， ７５％）
（Ｃ）の物性；
^１Ｈ−ＮＭＲ（４００ ＭＨｚ，ＣＤＣｌ_３）
０．８８ （１８Ｈ， ｔ， Ｊ＝６．５ Ｈｚ）
１．２７―１．４９ （１０８Ｈ， ｍ）
１．７６ （４Ｈ， ｑｕｉｎ， Ｊ＝６．５ Ｈｚ）
１．８４ （８Ｈ， ｑｕｉｎ， Ｊ＝６．５ Ｈｚ）
４．０５ （４Ｈ， ｔ， Ｊ＝６．５ Ｈｚ）
４．０７ （８Ｈ， ｔ， Ｊ＝６．５ Ｈｚ）
７．１８ （４Ｈ， ｓ）
７．４６ （２Ｈ， ｄ， Ｊ＝１２．６ Ｈｚ）
７．４７ （２Ｈ， ｄ， Ｊ＝１０．６ Ｈｚ）
７．５９ （２Ｈ， ｄ， Ｊ＝１２．６ Ｈｚ）
９．２６ （２Ｈ， ｄ， Ｊ＝１０．６ Ｈｚ）
１０．２６ （２Ｈ， ｓ）
ＦＡＢ ＭＳ （マススペクトル ７０ｅＶ） ｍ／ｚ １５５４ （Ｍ＋Ｈ）
元素分析値（測定値）Ｃ， ７７．４８； Ｈ， １０．５２； Ｎ，１．７０％
（理論値）Ｃ_１００Ｈ_１６４Ｎ_２Ｏ_１０: Ｃ， ７７．２７ ； Ｈ， １０．６３； Ｎ， １．８０％
紫外・可視吸収スペクトルλ（溶媒：クロロホルム）＝２７０ （ε＝３６０００）， ２７９ （ｓ， ε＝３３０００）， ３６５ （ε＝２４０００）， ４１８ （ε＝３７０００）， ４３９ （ｓ，ε＝３２０００） ｎｍ
【００３４】
実施例６
実施例５で得られた２，２’−ビス（３，４，５−トリドデシルオキシベンゾイルアミノ）−５，５’−ビトロポン（Ｃ）を、濃度が１重量％となるよう各種有機液体を添加した試験管に入れ、約７０℃に加熱後、常温（２５℃）にて静置冷却したときの状態を観察し、このときの内容物の流動性の有無、また流動性のないものについてはゲル化物の固さを調べた。実施例２と同様に４段階評価、すなわち、◎：流動性なし、ゲル化物は均一で固い、○：流動性なし、ゲル化物は均一で軟らかい、△：流動性ややあり、×：不均一混合物または均一だが流動性あり、を行った。比較として、公知ゲル化剤である１２−ヒドロキシステアリン酸に関しても同様の方法で評価した。２，２’−ビス（３，４，５−トリドデシルオキシベンゾイルアミノ）−５，５’−ビトロポン（Ｃ）と１２−ヒドロキシステアリン酸をゲル化剤として用いた実験結果を以下の表４に示す。
【００３５】
【表４】

【００３６】
一般式１および一般式２における化合物における、環ＡおよびＢにおける置換基Ｘ、ＹおよびＺとしては、それぞれ独立に、Ｈ、アルキル基、アルコキシ基およびチオアルキル基などが挙げられる。 具体的には、アルキル基としてはエチル基、ブチル基、ヘキシル基、オクチル基、ドデシル基など、炭素数１〜２０のアルキル基が挙げられる。アルコキシ基としてはエトキシ基、ブトキシ基、ヘキシルオキシ基、オクチルオキシ基、ドデシルオキシ基など、炭素数１〜２０のアルコキシ基が挙げられる。チオアルキル基としてはエチルチオ基、ブチルチオ基、ヘキシルチオ基、オクチルチオ基、ドデシルチオ基など、炭素数１〜２０のアルキルチオ基が挙げられる。これらのアルキル基や、アルコキシ基およびアルキルチオ基におけるアルキル部分は、直鎖でも分岐していても良いが、好ましくは直鎖である。また、アルキル部分が比較的長鎖である方が好ましく、炭素数はいずれも６以上であることが好ましい。
これらの置換基の中でも好ましいのはアルキル基またはアルコキシ基であり、より好ましくはアルコキシ基である。環Ａ，Ｂにおける置換基の位置および数に制限はないが、好ましくはカルボニル基に対してｍ−位（４カ所）およびｐ−位（２カ所）のいずれかであり、これら６カ所に置換基を有する場合がより好ましい。
【００３７】
ゲル硬度については、ゲル調製後、逆さに試験管を立てて、１時間後、ゲルの重さに耐えられ、そのままの状態のものを硬いものと評価した。
【００３８】
前記一般式１に属する化合物群を以下に例示する。
Ｙの位置に置換基を有する化合物群Ａ
【００３９】
【化９】

【００４０】
【化１０】

【００４１】
【化１１】

【００４２】
【化１２】

【００４３】
【化１３】

【００４４】
【化１４】

【００４５】
【化１５】

【００４６】
【化１６】

【００４７】
【発明の効果】
本発明によれば、前記一般式１および２で示される、動植物油脂、エステル、アルコール、炭化水素系油剤など幅広い有機液体に対し、また廃食用油、廃潤滑油、廃金属加工油剤、香料、植物精油、揮散性消臭剤、抗菌性薬剤などに対して、少量の添加で均一で良好なゲル化物または固化物を形成できる、新規な低分子有機ゲル化または固化剤を提供するという顕著な効果がもたした。更に、前記新規化合物を有効成分とする新規なゲル状芳香剤組成物、ゲル状揮散性消臭剤組成物、ゲル状抗菌性薬剤組成物などは長期間に亘って徐放させることができる有用なゲル状薬剤を提供できたという、顕著な効果がもたらした。[0001]
BACKGROUND OF THE INVENTION
The present invention provides a novel compound represented by the general formula 1 and the general formula 2, an organic liquid gelling or solidifying agent containing at least each of the novel compounds as an organic low-molecular gelling agent or a solidifying agent, and the novel Organic low molecular weight gelling agent or solidifying agent and at least one animal and vegetable oil, ester, alcohol, hydrocarbon oil, sustained release fragrance, sustained release vegetable essential oil, volatile deodorant and volatile antibacterial The present invention relates to a gelled or solidified product comprising a gelled or solidified component selected from the group consisting of drugs.
[0002]
[Prior art]
Examples of the organic liquid gelling agent include those made of a polymer material and those made of an organic low molecular weight compound. Development of the latter is relatively slow compared to the former, and many organic low-molecular gelling agents have been proposed so far. The gelling agent means a compound having a function of giving a yield value to the system and eliminating the fluidity of the system when added to an organic liquid.
Gelling agents or solidifying agents are perfumes, cosmetics, pharmaceuticals, paints, inks, lubricants, agriculture, fisheries, and industrial fields including various battery processing fields such as fibers, resins, polymers, rubbers, metals, etc. In order to control fluidity and prevent liquid evaporation, it is used as a viscosity modifier, etc., and as a solidifying agent for easy and efficient recovery and disposal, and reuse of waste solvent as fuel. Yes. Various organic liquids to be gelled or solidified are used in relation to the above-mentioned applications and treatment targets, but animal and vegetable oils, esters, polyols, ethers, alcohols, hydrocarbons, etc. are mainly used in the above fields. It is used.
[0003]
[Patent Document 1]
Japanese Patent Publication No. 60-54092, Claims [Patent Document 2]
Japanese Patent Publication No.49-7268, Claims [Patent Document 3]
JP-A-55-75493, Claims [Patent Document 4]
Japanese Patent Publication No. 54-33798, Claims [Patent Document 5]
Japanese Patent Laid-Open No. 5-320617, Claims [Patent Document 6]
Japanese Patent Laid-Open No. 8-231942 and claims (Patent Document 7)
Japanese Patent Laid-Open No. 2002-128749, Claims
Examples of the organic low-molecular gelling agent or solidifying agent include 12-hydroxystearic acid (Patent Document 1), dibenzylidene sorbitol (Patent Document 2), aromatic nucleus substitution products thereof, and alkali metals of fatty acids (Patent Document 3). And alkaline earth metal salts, acylated amino acid amides (Patent Document 4), cholesterol derivatives, bisamides (Patent Document 5), dialkylurea derivatives (Patent Document 6), and the like. However, among these, 12-hydroxystearic acid is inexpensive, but there are few types of organic liquids that can be gelled or solidified, and the temperature at which the resulting gel softens is low, and dibenzylidene sorbitol is a small amount. However, it is difficult to solidify short-chain alcohols with a low boiling point because of its high melting point, and the alkali metal of fatty acids. The salt / alkaline earth metal salt has a problem in that it requires a large amount of addition for gelation or solidification, and there are restrictions such as limited usable conditions.
[0005]
In such a situation, Akira Mori et al. In the above-mentioned Patent Document 7, against the conventional gelling or solidifying agent, for the organic liquid or waste edible oil, waste lubricant oil, waste metal processing oil, etc. A cyanotropolone derivative has been proposed as a gelling or solidifying agent that produces a uniform and good gelled product or solidified product with a small amount of addition. However, the synthesis of cyanotropone derivatives is not only time consuming and troublesome because of many operations, but also has the disadvantage that tropolone, which is a raw material for cyanotropone derivatives, is expensive.
Further, since the properties required for the gelling or solidifying agent are different in relation to the intended use, it is desired to develop the material having properties suitable for the intended use.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to produce an organic liquid that is easy to manufacture, can be gelled or solidified with a small amount of addition of various organic liquids, and is highly stable against long-term storage and temperature changes. Alternatively, a solidifying agent and a useful new compound and a novel gelling or solidifying agent containing the novel compound as an active ingredient are provided. In order to solve the above problems, in studying a novel compound that functions as a gelling or solidifying agent for an organic liquid, the compound represented by the general formula 1 or the general formula 2 is It was found that the functionality as a solidifying or solidifying agent was improved, and the above problems could be solved.
[0007]
[Means for Solving the Problems]
The first of the present invention is a novel gelling agent or solidifying agent comprising an N, N′-dibenzoylurea derivative represented by the general formula 1 and a 5,5′-bitropone derivative represented by the general formula 2 .
[0008]
[Chemical 3]

[0009]
[Formula 4]

[0010]
In the above general formulas 1 and 2, X, Y and Z are independently selected from H, C _m H _{2m + 1} , OC _n H _{2n + 1} and SC _q H _{2q + 1} . m, n and q are integers of 1 to 20, and each m, n and q are independently selected.
[0011]
The second of the present invention, N represented before following general formula 1, N'-dibenzoyl urea derivatives or at least one animal or vegetable fats and oils and novel gelling or solidifying agent comprising a compound of the general formula 2, ester Including a gelled or solidified component selected from the group consisting of alcohol, hydrocarbon oils, sustained release fragrances, sustained release plant essential oils, volatile deodorants, and volatile antibacterial agents It is a solidified or solidified product. Preferably, at least one gelled or solidified component is α-pinene, β-pinene, limonene, linalool, geraniol, citral, squalene, karen, α-farnesene, β-farnesene, α-guaien, d-guaien , α- caryophyllene, β- caryophyllene, d- cadinene, γ- cadinene, α- Bizabore down, γ- Bizaboren, α- cedrene, β- cedrene, valencene, thujopsene, Tapinen, nerol, citronellol, farnesol, neroli Doll, α -Visabolol, β-caryophyllene alcohol, α-santalol, β-santalol, vetiverol, cedrol, ethylhexanoate, cis-3-hexenol, alcohol C-6, linalyl acetate, neryl acetate, citral, citronellal, ta Gelled or solidified product as described above, characterized in that it is a fragrance selected from the group consisting of pinole and methyl ionone, (2) jasmine oil, rose oil, turpentine oil, orange oil, bergamot oil, ylang ylang oil, hanamas Oil, lavender oil, geranium oil, citronella oil, sage oil, peppermint oil, spearmint oil, lemon oil, lemongrass oil, rosemary oil, basil oil, clove oil, coriander oil, eucalyptus oil, geranium oil, ginger oil, grapefruit A plant essential oil selected from the group consisting of oil, hiba oil, cypress oil, lavandin oil, thyme oil, lime oil, cinnamon leaf oil, mint oil, anise oil, petitgren oil, laurel oil, pine oil, mint oil and zerel oil The gelation or Phased product or (3) pyruvate esters, wherein the gelled or solidified product, which is a volatile agent selected from the group consisting of hinokitiol and ants thioisocyanate.
[0012]
[Embodiments of the present invention]
The present invention will be described in more detail.
I. The N, N′-dibenzoylurea derivative represented by the general formula 1 of the present invention is made from urea and chlorobenzoic acid of 2 equimolar amount or more, and is a suitable alkali catalyst such as 4-dimethylaminopyridine (DMAP). Can be converted to an amide compound by reaction in a reaction medium such as pyridine. This reaction can be carried out by reacting at 0 to 100 ° C. for 1 to 12 hours.
Examples of the alkali catalyst include sodium hydride, triethylamine, 1,5-diabicyclo [4.3.0] non-5-ene, 1,8-diabicyclo [5.4.0] undec-7-ene in addition to the above DMAP. And potassium carbonate and sodium carbonate. In addition to the pyridine, the reaction medium includes ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene and xylene, hexamethylene phosphate triamide, dimethyl sulfoxide, N-methylpiperidine, N- Examples include methylpyrrolidine and picoline.
In the reaction process, when unreacted raw materials and by-products remain in the reaction product, the reaction product can be purified by known means such as distillation under reduced pressure or solvent fractionation. For example, the reaction product can be purified by removing unreacted substances under reduced pressure, recrystallization with an organic solvent such as ethyl acetate or hexane, adsorption treatment of activated clay, activated carbon, silica gel, alumina, etc. These may be applied alone or in combination as necessary.
The compound of the general formula 2 can be similarly synthesized by replacing urea with the following compound W.
[0013]
[Chemical formula 5]

[0014]
II. The novel compounds of the above general formula 1 include processing fields such as perfumes, pharmaceuticals, cosmetics, paints, inks, lubricants, agriculture, fisheries and various battery electrolytes, fibers, resins, polymers, rubbers, metals, etc. It is useful as a gelling or solidifying agent for various organic liquids used in the industry.
Examples of the organic liquid include sesame oil, soybean oil, rapeseed oil, corn oil, safflower oil, sunflower oil, cottonseed oil, olive oil, palm oil, castor oil, fish oil, pork oil, beef tallow and other animal and vegetable oils, isopropyl myristate, Esters such as -2-ethylhexanoic acid glyceride and 2-octyldodecyl myristylate, alcohols such as methanol, ethanol and decanol, hydrocarbon oils such as kerosene, light oil, heavy oil, liquid paraffin and isoparaffin, hexane and dodecane It is possible to target waste oils that are recovered or reused, such as organic solvents, waste cooking oils, waste lubricating oils, waste metal processing oils, and the like.
[0015]
In addition, the novel compound of the general formula 1 is also useful for the production of a sustained-release drug preparation in which a fragrance, a plant essential oil, a volatile deodorant, an antibacterial drug or the like is gelled or solidified.
The fragrance may be a single fragrance or a blended fragrance. Specifically, α-pinene, β-pinene, limonene, linalool, geraniol, citral, squalene, carene, α-farnesene, β-farnesene, α-guanene, d-guaien, α-caryophyllene, β-caryophyllene, d -Cadinene, γ-Cadinene, α-Bisabolene, β-Bisabolene, γ-Bisabolene, α-Cedrene, β-Cedrene, Valencene, Tuyopsen, Tarpinene, Nerol, Citronellol, Farnesol, Nerolidol, α-Visaborol, β-Caryophyllene Alcohol , Α-santalol, β-santalol, vetiverol, cedrol, ethylhexanoate, cis-3-hexenol, alcohol C-6, linalyl acetate, neryl acetate, citronellal, terpineol, methyl ionone, etc. Can.
[0016]
Among the plant essential oils, jasmine oil, rose oil, turpentine oil, orange oil, bergamot oil, ylang ylang oil, hanamas oil, lavender oil, geranium oil, citronella oil, sage oil, peppermint oil, spearmint oil, lemon oil, lemongrass Oil, rosemary oil, basil oil, clove oil, coriander oil, eucalyptus oil, geranium oil, ginger oil, grapefruit oil, hiba oil, cypress oil, lavandin oil, thyme oil, lime oil, cinnamon leaf oil, peppermint oil, anise And oil, petitgren oil, laurel oil, pine oil, mint oil, zerel oil and the like.
[0017]
Examples of the volatile deodorant include pyruvate esters such as ethyl pyruvate and phenylethyl pyruvate described in JP-A-6-121822, and examples of the antibacterial agent include hinokitiol and allylthioisocyanate. .
[0018]
III. The method of using the gelling or solidifying agent of the present invention is as follows. The gelling or solidifying agent of the present invention is added to 1 mL of the organic liquid, fragrance, vegetable essential oil, volatile deodorant or antibacterial agent. Add 0.1 to 50 mg, preferably 0.3 to 20 mg as dibenzoylurea derivative, heat to about 60 to 120 ° C. if desired, stir until uniform, and leave at room temperature to gelate Alternatively, the solidified product can be adjusted.
In addition, the gelling or solidifying agent of the present invention can be used alone, but is used in combination with known gelling agents, solidifying agents such as natural wax or synthetic wax, etc., as long as the properties of the gelling or solidifying agent of the present invention are not reduced. May be.
[0019]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not interpreted limitedly by this illustration.
Example 1
Synthesis of N, N′-di (3,4,5-tridodecyloxybenzoyl) urea (Compound B) according to Scheme 1 below;
[0020]
[Chemical 6]

[0021]
To 3,4,5-tridodecyloxybenzoic acid (810 mg, 1.2 mmol), 3 mL of thionyl chloride was added and heated under reflux for 3 hours, and then thionyl chloride was distilled off to obtain 3,4,5-tridodecyloxybenzoyl chloride. (A) was obtained. Urea (30 mg, 0.5 mmol) and 4-dimethylaminopyridine (DMAP, 12.2 mg, 0.1 mmol) are dissolved in 5 mL of pyridine, and 3,4,5-tridodecyloxybenzoyl chloride (A) is added thereto. Stir at room temperature for 6 hours. Then, saturated potassium hydrogen sulfate aqueous solution was added, extracted with chloroform (three times), and dried with sodium sulfate. The solvent was distilled off, and the residue was separated and purified by silica gel column chromatography (developing solvent: chloroform) to obtain N, N′-di (3,4,5-tridodecyloxybenzoyl) urea (B). (Yield 584 mg, 85%)
[0022]
Physical properties of (B);
¹ H-NMR (400 MHz, CDCl ₃ )
0.88 (18H, t, J = 7.0 Hz)
1.26 to 1.52 (108H, m)
1.75 (4H, quin, J = 6.6 Hz)
1.84 (8H, quin, J = 6.6 Hz)
4.05 (4H, t, J = 6.6 Hz)
4.06 (8H, t, J = 6.6 Hz)
7.14 (4H, s)
FAB MS (mass spectrum 70 eV) m / z 1374 (M + H)
Elemental analysis value (measured value) C, 75.93; H, 11.38; N, 1.99%
(Theoretical value) C ₈₇ H ₁₅₆ N ₂ O ₉ : C, 76.04; H, 11.44; N, 2.04%
[0023]
Example 2
Each organic solvent described in Table 1 was used so that the concentration of N, N′-di (3,4,5-tridodecyloxybenzoyl) urea (B) obtained in Example 1 was 2% by weight. And put it in a test tube, and after heating to about 70 ° C., the state of standing and cooling at room temperature (25 ° C.) is observed. In the case of no gel, the gelled product was evaluated as being hard after the preparation of the gel, with a test tube placed upside down, and after 1 hour, withstanding the weight of the gel. Evaluation is a four-level evaluation, that is, ◎: no fluidity, gelled product is uniform and hard, ○: no fluidity, gelled product is uniform and soft, △: somewhat fluid, ×: heterogeneous mixture or uniform but fluid There was sex, and went. The experimental results are shown in Table 1 below.
[0024]
[Table 1]

[0025]
Example 3
Test in which various perfumes and plant essential oils were added so that the concentration of N, N′-di (3,4,5-tridodecyloxybenzoyl) urea (B) obtained in Example 1 was 0.5% by weight. Put in a tube, heat to about 80 ° C to 100 ° C, and observe the state when it is allowed to cool at room temperature (25 ° C). Whether the contents are fluid or not fluid Examined the hardness of the gelled product. As in Example 2, four-level evaluation, ie, ◎: no fluidity, gelled product is uniform and hard, ○: no fluidity, gelled product is uniform and soft, Δ: somewhat fluid, ×: heterogeneous mixture Or it was uniform but fluid. Furthermore, the presence or absence of the fragrance of the gelled product was evaluated in two stages, that is, ◎: scented, ×: no scented. The experimental results are shown in Table-2.
[0026]
[Table 2]

[0027]
From the above results, N, N′-di (3,4,5-tridodecyloxybenzoyl) urea (B) is an effective gelling agent for the various organic liquids, Are also preferred gelling agents. Moreover, it became clear that a uniform and smooth gel compound was formed with respect to the said fragrance | flavor and vegetable oil.
[0028]
Example 4: The usefulness as a sustained-release solidified product is shown.
N, N′-di (3,4,5-tridodecyloxybenzoyl) urea (B) obtained in Example 1 is placed in a test tube to which lavender oil is added so that the concentration becomes 0.3% by weight. The change in the weight of the gelated product with the passage of time (0, 7, 15, 37 days) when heated to about 80 ° C. to 100 ° C. and then allowed to cool at room temperature was examined. Moreover, the state of the gelled material with progress of time was observed, the presence or absence of the fluidity of the contents at this time, and the non-fluidity of the gelled material were examined. As in Example 2, four-level evaluation, ie, ◎: no fluidity, gelled product is uniform and hard, ○: no fluidity, gelled product is uniform and soft, Δ: somewhat fluid, ×: heterogeneous mixture Or it was uniform but fluid. Furthermore, the presence or absence of the fragrance of the gelled product was evaluated in two stages, that is, ◎: scented, ×: no scented. For comparison, the change in weight of lavender oil with time (0, 7, 15, 37 days) was examined. The experimental results are shown in Table-3.
[0029]
[Table 3]

[0030]
Example 5
Synthesis according to scheme 2 of compounds of the following formula C belonging to general formula 2;
[0031]
[Chemical 7]

[0032]
[Chemical 8]

[0033]
To 3,4,5-tridodecyloxybenzoic acid (810 mg, 1.2 mmol), 3 ml of thionyl chloride was added and heated under reflux for 3 hours. Thionyl chloride was distilled off to obtain 3,4,5-tridodecyl chloride. Oxybenzoyl (Compound A) was obtained. 2,2'-diamino-5,5'-vitropone (120 mg, 0.5 mmol) and 4-dimethylaminopyridine (DMAP, 12.2 mg, 0.1 mmol) were dissolved in 5 ml of pyridine. 3,4,5-Tridodecyloxybenzoyl chloride was added and stirred at room temperature for 6 hours. Then, saturated potassium hydrogen sulfate aqueous solution was added, extracted with chloroform (three times), and dried with sodium sulfate. The solvent was distilled off, and the residue was separated and purified by silica gel column chromatography (developing solvent: chloroform), and 2,2′-bis (3,4,5-tridodecyloxybenzoylamino) -5,5′-vitropone (C ) (Yield 583 mg, 75%)
Physical properties of (C);
¹ H-NMR (400 MHz, CDCl ₃ )
0.88 (18H, t, J = 6.5 Hz)
1.27-1.49 (108H, m)
1.76 (4H, quin, J = 6.5 Hz)
1.84 (8H, quin, J = 6.5 Hz)
4.05 (4H, t, J = 6.5 Hz)
4.07 (8H, t, J = 6.5 Hz)
7.18 (4H, s)
7.46 (2H, d, J = 12.6 Hz)
7.47 (2H, d, J = 10.6 Hz)
7.59 (2H, d, J = 12.6 Hz)
9.26 (2H, d, J = 10.6 Hz)
10.26 (2H, s)
FAB MS (mass spectrum 70 eV) m / z 1554 (M + H)
Elemental analysis (measured value) C, 77.48; H, 10.52; N, 1.70%
_{(Theoretical) C 100 H 164 N 2 O} 10: C, 77.27; H, 10.63; N, 1.80%
UV / visible absorption spectrum λ (solvent: chloroform) = 270 (ε = 36000), 279 (s, ε = 33000), 365 (ε = 24000), 418 (ε = 37000), 439 (s, ε = 32000) nm
[0034]
Example 6
The 2,2′-bis (3,4,5-tridodecyloxybenzoylamino) -5,5′-vitropone (C) obtained in Example 5 was mixed with various organic liquids so that the concentration became 1% by weight. Place in the added test tube, heat to about 70 ° C, and then cool at room temperature (25 ° C) and observe the state of the contents at this time, whether the contents are fluid or not fluid Examined the hardness of the gelled product. As in Example 2, four-level evaluation, ie, ◎: no fluidity, gelled product is uniform and hard, ○: no fluidity, gelled product is uniform and soft, Δ: somewhat fluid, ×: heterogeneous mixture Or it was uniform but fluid. For comparison, 12-hydroxystearic acid, which is a known gelling agent, was also evaluated in the same manner. Table 4 below shows the experimental results using 2,2′-bis (3,4,5-tridodecyloxybenzoylamino) -5,5′-vitropone (C) and 12-hydroxystearic acid as gelling agents. Show.
[0035]
[Table 4]

[0036]
Examples of the substituents X, Y, and Z in the rings A and B in the compounds represented by the general formulas 1 and 2 include H, an alkyl group, an alkoxy group, and a thioalkyl group. Specifically, examples of the alkyl group include alkyl groups having 1 to 20 carbon atoms such as an ethyl group, a butyl group, a hexyl group, an octyl group, and a dodecyl group. Examples of the alkoxy group include an alkoxy group having 1 to 20 carbon atoms such as an ethoxy group, a butoxy group, a hexyloxy group, an octyloxy group, and a dodecyloxy group. Examples of the thioalkyl group include an alkylthio group having 1 to 20 carbon atoms such as an ethylthio group, a butylthio group, a hexylthio group, an octylthio group, and a dodecylthio group. These alkyl groups and the alkyl part in the alkoxy group and alkylthio group may be linear or branched, but are preferably linear. Moreover, it is preferable that the alkyl part is a relatively long chain, and it is preferable that the number of carbon atoms is 6 or more.
Among these substituents, an alkyl group or an alkoxy group is preferable, and an alkoxy group is more preferable. There is no limitation on the position and number of substituents in the rings A and B, but it is preferably one of the m-position (4 positions) and the p-position (2 positions) with respect to the carbonyl group. More preferably, it has a group.
[0037]
Regarding gel hardness, after preparing the gel, a test tube was set upside down, and after 1 hour, the weight of the gel was withstood, and the one in the state was evaluated as hard.
[0038]
Examples of the compounds belonging to the general formula 1 are shown below.
Compound group A having a substituent at the Y position
[0039]
[Chemical 9]

[0040]
[Chemical Formula 10]

[0041]
Embedded image

[0042]
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[0043]
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[0044]
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[0045]
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[0046]
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[0047]
【The invention's effect】
According to the present invention, a wide variety of organic liquids such as animal and vegetable oils and fats, esters, alcohols and hydrocarbon oils represented by the above general formulas 1 and 2, and waste edible oils, waste lubricating oils, waste metal processing oils, fragrances, Prominently to provide a novel low molecular organic gelling or solidifying agent capable of forming a uniform and good gelled product or solidified product with a small amount of addition to plant essential oil, volatile deodorant, antibacterial agent, etc. It was effective. Furthermore, a novel gel-like fragrance composition, a gel-like volatile deodorant composition, a gel-like antibacterial agent composition, etc., containing the above-mentioned novel compound as an active ingredient can be used for a sustained release over a long period of time. It was possible to provide an excellent gel-like drug.

Claims (5)

A novel gelling agent or solidifying agent comprising an N, N′-dibenzoylurea derivative represented by the general formula 1 or a 5,5′-bitropone derivative represented by the general formula 2.

In the general formulas 1 and 2, X, Y, and Z are independently selected from H, C _m H _{2m + 1} , OC _n H _{2n + 1} , and SC _q H _{2q + 1} . m, n and q are integers of 1 to 20, and each m, n and q are independently selected. A novel gelling agent or solidifying agent comprising an N, N'-dibenzoylurea derivative represented by the general formula 1 according to claim 1 or the compound of the general formula 2 and at least one animal or vegetable oil, ester, alcohol, Gelation or solidification comprising a hydrocarbon-based oil, a sustained-release fragrance, a sustained-release vegetable essential oil, a volatile deodorant, and a gelled or solidified component selected from the group consisting of a volatile antibacterial agent Product. At least one gelled or solidified component is α-pinene, β-pinene, limonene, linalool, geraniol, citral, squalene, carene, α-farnesene, β-farnesene, α-guanene, d-guaien, α- caryophyllene, beta-caryophyllene, d-cadinene, .gamma. cadinene, alpha-Bizabore emissions, gamma - Bizaboren, alpha-cedrene, beta-cedrene, valencene, thujopsene, Tapinen, nerol, citronellol, farnesol, nerolidol, alpha-Bizabororu, beta-caryophyllene alcohol, alpha-santalol, beta-santalol, vetiverol, cedrol, ethyl hexanoate, cis-3-hexenol, alcohol C-6, linalyl acetate, neryl acetate, citral, citronellal, Tapineo And gelled or solidified product according to claim 2, characterized in that from the group consisting of methyl ionone a perfume of choice. At least one gelled or solidified component is jasmine oil, rose oil, turpentine oil, orange oil, bergamot oil, ylang ylang oil, hanamas oil, lavender oil, geranium oil, citronella oil, sage oil, peppermint oil, spearmint Oil, Lemon oil, Lemongrass oil, Rosemary oil, Basil oil, Clove oil, Coriander oil, Eucalyptus oil, Geranium oil, Ginger oil, Grapefruit oil, Hiba oil, Cypress oil, Labandin oil, Thyme oil, Lime oil, Cinnamon Gelatinized or solidified according to claim 2, characterized in that it is a plant essential oil selected from the group consisting of leaf oil, mint oil, anise oil, petitgren oil, laurel oil, pine oil, mint oil and zerel oil Product. The gelled or solidified product according to claim 2, wherein the at least one gelled or solidified component is a volatile agent selected from the group consisting of pyruvate, hinokitiol and allylthioisocyanate. .