JP4350288B2 - Method for producing betaine ester - Google Patents

Description

【００１８】
（式中、Ｘは塩素原子又は臭素原子であり、Ａは炭素数１〜３の直鎖又は分岐鎖のアルキレン基であり、Ｒは炭素数１〜４のアルキル基又はアルケニル基である。）
で表される化合物が好ましい。具体的には、クロロ酢酸メチル、クロロ酢酸エチル、クロロ酢酸プロピル、クロロ酢酸ブチル、ブロモ酢酸エチル、ブロモ酢酸メチル、２−クロロプロピオン酸メチル、２−クロロプロピオン酸エチル、２−クロロプロピオン酸プロピル、２−クロロプロピオン酸ブチル、２−ブロモプロピオン酸メチル、２−ブロモプロピオン酸エチル、２−ブロモプロピオン酸プロピル、２−ブロモプロピオン酸ブチル等が好ましく、クロロ酢酸エチル、クロロ酢酸メチル、２−クロロプロピオン酸メチルがより好ましいが、クロロ酢酸エチルが減圧留去が容易である点で特に好ましい。
【００１９】
［３級アミン］
本発明の３級アミンは、少なくとも１個以上の３級アミノ基を有するものが好ましく、３級アミノ基の窒素原子上の置換基のうち少なくとも一つはメチル基又はエチル基であり、且つ１級又は２級アミノ基を持たないものがより好ましい。これらの３級アミンの中では、一般式(II)、(III)又は(IV)
【００２０】
【化３】

【００２１】
（式中、Ｒ¹は炭素数１〜３０の１価の飽和又は不飽和脂肪族炭化水素基、芳香族炭化水素基あるいは脂環式炭化水素基を示し、Ｒ²及びＲ³はそれぞれメチル基又はエチル基を示し、Ｒ⁴ＣＯ−は炭素数１〜３０のアシル基、Ｒ⁵は炭素数１〜３のアルキレン基を示し、Ｒ⁶及びＲ⁷はそれぞれメチル基又はエチル基を示す。。）
で表される３級アミン、特にジメチルアルキルアミン（アルキル基の炭素数１〜３０）、アルカノイルアミノプロピルジメチルアミン（アルカノイル基の炭素数２〜３０）、N,N,N',N'−テトラアルキル−1,3−ジアミノプロパン（アルキル基の炭素数１〜２）が好ましい。
【００２２】
これらの好ましい３級アミンの具体例としては、トリメチルアミン、エチルジメチルアミン、プロピルジメチルアミン、ブチルジメチルアミン、ヘキシルジメチルアミン、オクチルジメチルアミン、デシルジメチルアミン、ドデシルジメチルアミン、テトラデシルジメチルアミン、ヘキサデシルジメチルアミン、オクタデシルジメチルアミン、エイコサニルジメチルアミン、ドコサニルジメチルアミン、アセチルアミノプロピルジメチルアミン、プロパノイルアミノプロピルジメチルアミン、ブタノイルアミノプロピルジメチルアミン、ヘキサノイルアミノプロピルジメチルアミン、オクタノイルアミノプロピルジメチルアミン、デカノイルアミノプロピルジメチルアミン、ドデカノイルアミノプロピルジメチルアミン、テトラデカノイルアミノプロピルジメチルアミン、ヘキサデカノイルアミノプロピルジメチルアミン、オクタデカノイルアミノプロピルジメチルアミン、エイコサノイルアミノプロピルジメチルアミン、ドコサノイルアミノプロピルジメチルアミン、N,N,N',N'−テトラメチル−1,3−ジアミノプロパン等が挙げられる。
【００２３】
［エステル交換反応工程］
ベタインエステル（Ａ）とアルコール（ｂ）とのエステル交換反応におけるアルコール（ｂ）の仕込み量は、ベタインエステル（Ａ）に対して1〜10当量が好ましく、1〜2当量が未反応物を低減できる点でより好ましい。また、アルコール（ｂ）を前工程で溶媒として用いて残留している場合は、合計して上記範囲になることが好ましい。
【００２４】
エステル交換反応における、槽内温度は、１５〜１２０℃が好ましく、より好ましくは３０〜８０℃であり、特に４０〜６０℃が、反応後生成するアルコール（ａ）を容易に留出できる点で好ましい。また、槽内圧力は、生成するアルコール（ａ）及びアルコール（ｂ）の沸点にもよるが、0.00133〜13.3kPaが好ましく、0.133〜5.33kPaがより好ましい。
【００２５】
エステル交換反応において、必要に応じてエーテル、炭化水素等の一般にアルカリに安定な溶媒を用いることができる。例えば、前述のハロゲン化脂肪酸エステルの減圧留去時に用いることのできる溶媒が挙げられる。
【００２６】
エステル交換反応は触媒として塩基性触媒を使用するが、塩基性触媒としては、反応物との相溶性に優れた金属アルコキシド等が好ましく、アルカリ金属アルコキシドが、低温での反応性の点でより好ましい。アルカリ金属アルコキシドとしては、ナトリウムメトキシド、ナトリウムエトキシド、カリウムメトキシド、カリウムエトキシド、カリウム tert-ブトキシド等が好ましく、ナトリウムメトキシド及びアルコール（ｂ）のナトリウム又はカリウムアルコキシドが好ましい。
【００２７】
エステル交換時に添加する塩基性触媒の量は、ベタインエステル（Ａ）に対して0.1〜20倍モルが好ましく、より好ましくは1〜10倍モルであり、特に5〜10倍モルが好ましい。塩基性触媒の添加は、減圧・攪拌下で分割滴下する方法が好ましい。
【００２８】
エステル交換反応は、通常、塩基性触媒添加後、１時間から５時間以内に終了する。得られたベタインエステル（Ｂ）はその用途によって、溶媒留去や晶析等の精製を施しても構わないが、反応終了品をそのまま用いることもできる。
【００２９】
［アルコール（ｂ）］
本発明で用いられるアルコール（ｂ）は、アルコール（ａ）を除く炭素数２以上のアルコールであり、炭素数５以上、特に５〜１５の脂肪族１価アルコール、炭素数２以上、特に２〜１５の脂肪族多価アルコール、炭素数２以上、特に２〜２８の含フッ素アルコール、炭素数５以上、特に５〜１５の脂環式アルコール、炭素数６以上、特に６〜２０の芳香族アルコール、炭素数５以上、特に５〜９の複素環式アルコールが好ましい。更には、アルコール（ｂ）が単独で放出された時に、種々のトイレタリー商品等に付与できる機能を持つものが好ましく、特に、調合香料成分である香気性アルコール（１）、防菌防黴性を有する抗微生物性アルコール（２）、保湿性を有する保湿性アルコール（３）、生理活性を有する生理活性アルコール及び着色性を有する着色性アルコール（４）、一般的な表面活性を有する表面改質性アルコール（５）が好ましく、香気性アルコール（１）、抗微生物性アルコール（２）がより好ましい。
【００３０】
（１）香気性アルコールは、合成香料（化学工業日報社）記載の香料用途に用いられるアルコール等であり、以下のものが挙げられる。
【００３１】
・炭素数５〜１５の飽和又は不飽和の直鎖又は分岐鎖アルコール
青葉アルコール（cis-3-ヘキセノール）、3-オクテノール、9-デセノール、ゲラニオール、ネロール、シトロネロール、ロジノール、ファルネソール、ヒドロキシシトロネロール等。
【００３２】
・炭素数６〜１２の芳香族アルコール
ベンジルアルコール、β-フェニルエチルアルコール、シンナミックアルコール、γ-フェニルプロピルアルコール、アニスアルコール、フェノキシエチルアルコール、スチラリルアルコール、3-メチル-5-フェニルペンタノール、2,2-ジメチル-3-(3-メチルフェニル)-プロパノール等。
【００３３】
・炭素数８〜１５の飽和又は不飽和の環式アルコール
2,4-ジメチル-3-シクロヘキセン-1-メタノール、4-イソプロピルシクロヘキシルメタノール、1-(4-イソプロピルシクロヘキシル)エタノール、p-tert-ブチルシクロヘキサノール、o-tert-ブチルシクロヘキサノール、、L-メントール、、1-(2-t-ブチルシクロヘキシルオキシ)-2-ブタノール、ペンタメチルシクロヘキシルプロパノール、1-(2,2,6-トリメチルシクロヘキシル)-3-ヘキサノール、サンタロール、ベチベロール等。
【００３４】
（２）抗微生物性アルコールは、日本防菌防黴剤辞典（日本防菌防黴学会発行）記載の防菌防黴用に用いられるアルコール等であり、以下のものが挙げられる。
【００３５】
・炭素数３〜１５の脂肪酸多価アルコール
グリセロールモノラウレート、トリ（ヒドロキシメチル）ニトロメタン、2-ブロモ-2-ニトロプロパン-1,3-ジオール等。
【００３６】
・炭素数７〜９の複素環式アルコール
1,3-ビス（ヒドロキシメチル）-5,5´-ジメチルヒダントイン、ヘキサヒドロ-1,3,5-トリス（ヒドロキシエチル）-S-トリアジン等。
【００３７】
（３）保湿性アルコールは、一般に保湿効果の認められるアルコールであり、以下のものが挙げられる。
【００３８】
・炭素数２〜６の脂肪族多価アルコール
グリセリン、プロピレングリコール、エチレングリコール、ペンタエリスリトール、グルコース等。
【００３９】
（４）生理活性アルコール及び着色性アルコールは、水酸基を有するビタミン類、副腎皮質刺激ホルモン、フェロモン、カロチノイド等であり、以下のものが好ましい。
【００４０】
・炭素数１６〜４０の不飽和の鎖状又は環状の１価又は多価アルコール
ビタミンＡ₁、ビタミンＡ₂、リボフラビン、L-アスコルビン酸、ビタミンＤ₂、ビタミンＤ₃、ビタミンＤ₄、コルチコステロン、デヒドロコルチコステロン、デオキシコルチコステロン、ボンビコール、ビオラキサンチン、クリプトキサンチン、ゼアキサンチン、ルテイン、ルビキサンチン等。
【００４１】
・炭素数２０の芳香族アルコール
キニン、キニジン等。
【００４２】
（５）表面改質性アルコールとしては、以下のものが挙げられる。
【００４３】
・式（Ｖ）で表されるポリアルキレンアルキルエーテル
Ｒ¹¹−Ｏ−（Ｒ¹²Ｏ）_p−Ｈ （Ｖ）
（式中、Ｒ¹¹は、炭素数１〜２４、好ましくは１〜１８のアルキル基又はアルケニル基、Ｒ¹²は、炭素数２〜３の直鎖又は分岐鎖のアルキレン基、ｐは１〜２０、好ましくは１〜１０の数を示す。）
具体的には、エチレングリコールモノアルキルエーテル、ジエチレングリコールモノアルキルエーテル、プロピレングリコールモノアルキルエーテル、ポリオキシエチレンモノメチルエーテル、ポリオキシエチレンモノエチルエーテル、ポリオキシエチレンモノオレイルエーテル、ポリオキシプロピレンモノアルキルエーテル、ポリオキシエチレン−ポリオキシプロピレン共重合アルコールモノアルキルエーテル、ポリオキシブチレンモノアルキルエーテル等。
【００４４】
・式(VI)で表されるグリセリルエーテル
Ｒ¹³−Ｏ−ＣＨ₂−ＣＨ（ＯＲ¹⁴）−ＣＨ₂−Ｏ−Ｒ¹⁵ (VI)
［式中、Ｒ¹³、Ｒ¹⁴及びＲ¹⁵は、同一又は異なって、水素原子、又は式(VII)
Ｒ¹¹−Ｏ−（Ｒ¹²Ｏ）_q− (VII)
（Ｒ¹¹及びＲ¹²は前記と同じ意味を示し、ｑは０〜２０の数を示す。）
で表される基を示し、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵のうち少なくとも１つは水素原子で、且つ全てが同時に水素原子になることはない。］
具体的には、モノアルキルグリセリルエーテル、ジアルキルグリセリルエーテル、メチルトリエチレングリセリルエーテル等
・アルキル鎖が炭素数１〜１８のアルキルグリコシド
具体的には、α−メチルグリコシド、β−ドデシルグリコシド等。
【００４５】
・式(VIII)で表される含フッ素アルコール
Ｒ^f−（ＣＨ₂）_n−ＯＨ (VIII)
（式中、Ｒ^fは炭素数１〜２０の直鎖又は分岐鎖のアルキル基の水素原子の少なくとも１つがフッ素原子で置換されたフルオロアルキル基、ｎは１〜８の整数を示す。）
具体例として、2,2,3,3,3-ペンタフルオロプロパノール、2-（パーフルオロオクチル）エタノール、2-（パーフルオロデシル）エタノール、6-（パーフルオロエチル）ヘキサノール、6-（パーフルオロブチル）ヘキサノール、6-（パーフルオロヘキシル）ヘキサノール、6-（パーフルオロオクチル）ヘキサノール、6-（パーフルオロイソプロピル）ヘキサノール、4,4,4-トリフルオロブタノール、2,2,3,4,4,4-ヘキサフルオロブタノール、2,2,3,3-テトラフルオロプロパノール、1H,1H,5H-オクタフルオロペンタノール、1H,1H,7H-ドデカフルオロヘプタノール、1H,1H,9H-ヘキサデカフルオロノナノール、2-（パーフルオロ-3-メチルブチル）エタノール、2-（パーフルオロ-5-メチルヘキシル）エタノール、2-（パーフルオロ-7-メチルオクチル）エタノール、2-（パーフルオロ-9-メチルドデシル）エタノール、6-（パーフルオロ-1-メチルエチル）ヘキサノール、2-（パーフルオロ-3-メチルブチル）ヘキサノール、6-（パーフルオロ-5-メチルヘキシル）ヘキサノール、6-（パーフルオロ-7-メチルオクチル）ヘキサノール、4,4,4-トリフルオロ-2-ブテン-1-オール、1H,1H,2H,2H,3H,3H-パーフルオロノナノール等。
【００４６】
【実施例】
例中の部及び％は特記しない限り重量基準である。
【００４７】
実施例１：塩化 N,N-ジメチル-N-ゲラニルオキシカルボニルメチル-N-(3-(オクタデカノイルアミノ)プロピル)アンモニウムの製造
反応槽にN,N-ジメチル-N'-オクタデカノイル-1,3-ジアミノプロパン3.69kg (10mol)と99.5%エタノール２L(2.5kg)を仕込み、乾燥窒素雰囲気下で加熱溶解させ45℃で保温・攪拌しておき、これにクロロ酢酸エチル1.35kg (11mol)を滴下速度60mL/minで仕込み、槽内温度45±3℃で10時間攪拌した。反応混合物の¹H-NMRスペクトル(FT、200MHz)を測定し、原料アミン由来の吸収ピークが消失していることを確認後、槽内を減圧とし、乾燥窒素を0.2m³/hで吹き込みつつ、残ったクロロ酢酸エチル及びエタノールを減圧留去した。留分受器内に留出物が2.3Lまで溜まった時点で、槽内に乾燥窒素を導入して常圧とし槽内反応混合物の粘度を測定したところ、485mPa・sであり、粘度の増加傾向が認められ、反応物中のクロロ酢酸エチル残留量をガスクロマトグラフィーにより測定したところ1.6%であった。この時点でゲラニオール3.1kg(20mol)を仕込み、45℃で10分間攪拌し、反応物の粘度が250mPa・sであることを確認後、槽内物を薄膜式蒸留装置（スミス式）に移送した。蒸留器の壁温度49℃、圧力0.133kPaに設定し、さらに8時間、減圧蒸留をおこなった。蒸留器に残留する中間体のベタインエステルとゲラニオールの混合物中のクロロ酢酸エチル残留量をガスクロマトグラフィーを用いて測定したところ、検出下限（15mg/kg）未満であった。得られた淡黄色油状混合物を反応槽に移送し、槽内温度43±2℃、槽内圧力1.33〜2.67kPaにおいて、28%ナトリムメトキシドメタノール溶液408mLづつを40分間隔で計5回添加し、エステル交換反応を行なった。反応物のナトリウムメトキシドの有効分の添加総量は54g(1mol)であった。5回目のナトリウムメトキシドを添加して40分後に¹H-NMRスペクトルを測定したところエチルエステルに由来する吸収ピークは消失しており、ゲラニオールを18%含有する塩化 N,N-ジメチル-N-ゲラニルオキシカルボニルメチル-N-(3-(オクタデカノイルアミノ)プロピル)アンモニウムを40℃で粘度210mPa・sの淡褐色液体（25℃では淡褐色ワックス状物）として、7.31kg（10mol；収率100%）得た。このものに含まれるクロロ酢酸エチル及びクロロ酢酸ゲラニルの量は、GC及びGC/MASS定量により、ともに10mg/kg未満であった。
【００４８】
実施例2：1,3-ビス（塩化 N,N-ジメチル-N-ゲラニルオキシカルボニルメチルアンモニウム）プロパンの製造
反応槽にN,N,N',N'-テトラメチル-1,3-ジアミノプロパン2.6kg(20mol)と99.5%エタノール5L(4kg)を仕込み、乾燥窒素雰囲気下で加熱溶解させ45℃で保温・攪拌しておき、これにクロロ酢酸エチル2.69kg(22mol)を滴下速度60L/minで仕込み、槽内温度45±3℃で５時間攪拌した。反応混合物の¹H-NMRスペクトル(FT、200MHz)を測定し、原料アミン由来の吸収ピークが消失していることを確認後、槽内を減圧とし、乾燥窒素を0.2m³/hで吹き込みつつ、残ったクロロ酢酸エチル及びエタノールを減圧留去した。留分受器内に留出物が5Lまで溜まった時点で、槽内に乾燥窒素を導入して常圧とし槽内反応混合物の粘度を測定したところ、630mPa・sであり、粘度の増加傾向が認められ、反応物中のクロロ酢酸エチル残留量をガスクロマトグラフィーにより測定したところ2.8%であった。この時点でゲラニオール 7.7kg(50mol)を仕込み、４５℃で10分間攪拌し、反応物の粘度が490mPa・sであることを確認後、槽内物を薄膜式蒸留装置（スミス式）に移送した。蒸留器の壁温度49℃、圧力0.133kPaに設定し、さらに10時間、減圧蒸留をおこなった。蒸留器に残留する中間体のベタインエステルとゲラニオールの混合物中のクロロ酢酸エチル残留量をガスクロマトグラフィーを用いて測定したところ、検出下限（15mg/kg）未満であった。得られた淡黄色油状混合物を反応槽に移送し、槽内温度43±2℃、槽内圧力1.33〜2.66kPaで安定させた後、28%ナトリムメトキシドメタノール溶液81．6mLづつを40分間隔で計5回添加し、エステル交換反応を行なった。反応物のナトリウムメトキシドの有効分の添加総量は108g(2mol)であった。5回目のナトリウムメトキシドを添加して40分後に¹H-NMRスペクトルを測定したところエチルエステルに由来する吸収ピークは消失しており、ゲラニオールを11.5%含有する1,3-ビス（塩化 N,N-ジメチル-N-ゲラニルオキシカルボニルメチルアンモニウム）プロパンを40℃で粘度490mPa・sの淡褐色液体（25℃では淡褐色ワックス状物）として、13.4kg（20mol；収率100%）得た。このものに含まれるクロロ酢酸エチル及びクロロ酢酸ゲラニルの量は、GC/MASS定量により、ともに10mg/kg未満であった。
【００４９】
実施例3：塩化 N,N-ジメチル-N-メンチルオキシカルボニルメチル-N-(3-(オクタデカノイルアミノ)プロピル)アンモニウムの製造
反応槽にN,N-ジメチル-N'-オクタデカノイル-1,3-ジアミノプロパン3.69kg (10mol)と99.5%エタノール２L(2.5kg)を仕込み、乾燥窒素雰囲気下で加熱溶解させ45℃で保温・攪拌しておき、これにクロロ酢酸エチル1.35kg (11mol)を滴下速度60mL/minで仕込み、槽内温度45±3℃で10時間攪拌した。反応混合物の¹H-NMRスペクトル(FT、200MHz)を測定し、原料アミン由来の吸収ピークが消失していることを確認後、槽内を減圧とし、乾燥窒素を0.2m³/hで吹き込みつつ、残ったクロロ酢酸エチル及びエタノールを減圧留去した。留分受器内に留出物が2.3Lまで溜まった時点で、槽内に乾燥窒素を導入して常圧とし槽内反応混合物の粘度を測定したところ、500mPa・sであり、粘度の増加傾向が認められ、反応物中のクロロ酢酸エチル残留量をガスクロマトグラフィーにより測定したところ1.５%であった。この時点でメントール3.14kg(20mol)を仕込み、45℃で10分間攪拌し、反応物の粘度が250mPa・sであることを確認後、槽内物を薄膜式蒸留装置（スミス式）に移送した。蒸留器の壁温度49℃、圧力0.133kPaに設定し、さらに8時間、減圧蒸留をおこなった。蒸留器に残留する中間体のベタインエステルとメントールの混合物中のクロロ酢酸エチル残留量をガスクロマトグラフィーを用いて測定したところ、検出下限（15mg/kg）未満であった。得られた淡黄色油状混合物を反応槽に移送し、反応槽にリモネン10Lを加え、槽内温度70±2℃、槽内圧力1.33〜2.67kPaにおいて、28%ナトリムメトキシドメタノール溶液81.6mLづつを40分間隔で計5回添加し、エステル交換反応を行なった。反応物のナトリウムメトキシドの有効分の添加総量は108g(2mol)であった。5回目のナトリウムメトキシドを添加して40分後に¹H-NMRスペクトルを測定したところエチルエステルに由来する吸収ピークは消失した。槽内を50℃±2℃で、アセトン100Lを加え、50℃±2℃で1時間撹拌を行い均一溶液にした。この反応溶液を室温まで冷却し晶析を行い、大半のメントールとリモネンを除去した。結晶を減圧乾燥し、メントールを18%含有する塩化 N,N-ジメチル-N-メンチルオキシカルボニルメチル-N-(3-(オクタデカノイルアミノ)プロピル)アンモニウムを黄色結晶として、4.15kg（7.5mol；収率75%）得た。このものに含まれるクロロ酢酸エチル及びクロロ酢酸メンチルの量は、GC及びGC/MASS定量により、ともに10mg/kg未満であった。
【００５０】
実施例４：塩化 N,N,N-トリメチル-N-ゲラニルオキシカルボニルメチルアンモニウムの製造
反応槽に99.5%エタノール400ｇとクロロ酢酸エチル４２g (０．３４mol)を仕込み０℃に冷却した。トリメチルアミンをボンベより９０ｇ（１．５２モル）導入し０℃で10時間攪拌した。反応混合物を４５℃に昇温し、１．３３ｋＰａの減圧で残ったトリメチルアミン、クロロ酢酸エチル及びエタノールを減圧留去した。ゲラニオール７９ｇ(０．５mol)を仕込み、45℃で10分間攪拌し、反応物の粘度が250mPa・sであることを確認後、槽内物を薄膜式蒸留装置（スミス式）に移送した。蒸留器の壁温度49℃、圧力0.133kPaに設定し、さらに8時間、減圧蒸留をおこなった。蒸留器に残留する中間体のベタインエステルとゲラニオールの混合物中のクロロ酢酸エチル残留量をガスクロマトグラフィーを用いて測定したところ、検出下限（15mg/kg）未満であった。得られた淡黄色油状混合物を反応槽に移送し、槽内温度43±2℃、槽内圧力1.33〜2.67kPaにおいて、28%ナトリムメトキシドメタノール溶液１３ｇ（０．０７mol）づつを40分間隔で計5回添加し、エステル交換反応を行なった。反応物のナトリウムメトキシドの有効分の添加総量は18.4g(0.34mol)であった。5回目のナトリウムメトキシドを添加して40分後に¹H-NMRスペクトルを測定したところエチルエステルに由来する吸収ピークは消失しており、ゲラニオールを約18%含有する塩化 N,N,N-トリメチル-N-ゲラニルオキシカルボニルメチルアンモニウムを40℃で粘度210mPa・sの淡褐色液体（25℃では淡褐色ワックス状物）として、１２７ｇ（０．３４mol；収率100%）得た。このものに含まれるクロロ酢酸エチル及びクロロ酢酸ゲラニルの量は、GC及びGC/MASS定量により、ともに10mg/kg未満であった。
【００５１】
実施例５：塩化 N,N-ジメチル-N-ドデシル-N-ゲラニルオキシカルボニルメチルアンモニウムの製造
トリメチルアミン90ｇ（１．５２mol）の代わりにドデシルジメチルアミン66ｇ(０．３１mol)を用い４５℃で反応させた以外は実施例４と同様に行った。ゲラニオールを約1２%含有する塩化 N,N-ジメチル-N-ドデシル-N-ゲラニルオキシカルボニルメチルアンモニウムを淡褐色ワックス状物として、162ｇ（０．３１mol；収率100%）得た。このものに含まれるクロロ酢酸エチル及びクロロ酢酸ゲラニルの量は、GC及びGC/MASS定量により、ともに10mg/kg未満であった。
【００５２】
【発明の効果】
本発明によれば、これまで工業的に製造が困難であった高分子量アルコール、多価アルコール及び脱水・転位等の副反応を起こしやすいアルコール等のベタインエステルを高品質かつ安価で効率よく製造できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a betaine ester which has a function of releasing alcohol and is a useful compound for a fiber softener, a hair surface modifier and the like.
[0002]
[Prior art]
Conventional methods for producing betaine esters include (1) quaternization reaction (Menschutkin reaction) of tertiary amine and halogenated fatty acid ester of functional alcohol, and (2) acid catalyst of corresponding betaine and functional alcohol. (3) Reaction of betaine acid chloride with higher alcohols (US Pat. No. 2,888,383), (4) ω-amino acid alkyl ester as alkylating agent such as diazomethane And the like, and the like. However, these production methods have problems such that side reactions are liable to occur and a large amount of waste is produced as a by-product, making purification difficult.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to industrially easily obtain high-quality betaine esters such as high-molecular-weight alcohols, polyhydric alcohols, and alcohols that easily cause side reactions such as dehydration and rearrangement, which were difficult to produce by conventional methods. It is.
[0004]
[Means for Solving the Problems]
In the present invention, after reacting a halogenated fatty acid ester of a saturated or unsaturated monohydric alcohol having 1 to 4 carbon atoms (hereinafter referred to as alcohol (a)) with a tertiary amine, an unreacted halogenated fatty acid ester is converted into an unreacted halogenated fatty acid ester. Removing the betaine ester of alcohol (a) (hereinafter referred to as betaine ester (A)) and an alcohol having 2 or more carbon atoms excluding this betaine ester (A) and alcohol (a) (hereinafter referred to as alcohol (b)) ) In the presence of a basic catalyst to provide a betaine ester of alcohol (b) (hereinafter referred to as betaine ester (B)).
[0005]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the betaine ester means a structure in which a carboxyl group which is an acid form of betaine and an alcohol are esterified.
[0006]
[Production process of betaine ester (A)]
In the reaction step of obtaining a betaine ester (A) by reacting a halogenated fatty acid ester of alcohol (a) (hereinafter simply abbreviated as a halogenated fatty acid ester) with a tertiary amine, the halogenated fatty acid ester is compared with the tertiary amine. 1-10 equivalent is preferable, 1-3 equivalent is more preferable, 1.0-1.2 equivalent is especially preferable.
[0007]
The tertiary amine and the halogenated fatty acid ester may be added simultaneously, or the tertiary amine may be dropped into the halogenated fatty acid ester. In the case of adding a solvent, in the case of simultaneous addition, in the case of dropwise addition of a tertiary amine, it may be mixed with a tertiary amine or mixed with both a halogenated fatty acid ester and a tertiary amine. Good. When the tertiary amine is a low-boiling amine, it may be introduced as a gas into the halogenated fatty acid ester in the reaction vessel, or it may be cooled and liquefied and introduced into the pressure-resistant sealed reaction vessel simultaneously with the halogenated fatty acid ester. Alternatively, it may be dissolved in a solvent and introduced into the reaction vessel as a solution.
[0008]
The reaction temperature is preferably from 0 to 1550C, more preferably from 20 to 100 ° C in terms of suppressing side reactions, and particularly preferably from 40 to 80 ° C. When the viscosity increases at 80 ° C. or lower and hinders operations such as stirring and transfer, it is preferably diluted with a solvent described later.
[0009]
In the present invention, a solvent selected from an alcohol, an ether or ester having no hydroxyl group, and a hydrocarbon through a step of distilling off the unreacted halogenated fatty acid ester described below from the reaction step of obtaining the betaine ester (A). It is preferable to add. At this time, the addition amount of the solvent is preferably 10 to 100% by weight, more preferably 20 to 100% by weight with respect to the total charged amount.
[0010]
The alcohol used as the solvent is preferably methanol, ethanol, allyl alcohol, 1-propanol, 2-propanol or a mixed alcohol thereof, and more preferably the same alcohol as the alcohol (a) constituting the halogenated fatty acid ester.
[0011]
For ethers used as solvents, dimethyl ether, diethyl ether and tert-butyl methyl ether are used.For esters, methyl acetate and ethyl acetate are used.For hydrocarbons, pentane, hexane, heptane, petroleum ether, cyclohexane, toluene and limonene are used. It is preferable from the viewpoint of easiness of distillation and solubility.
[0012]
After completion of the reaction, unreacted halogenated fatty acid ester is removed by a method such as distillation under reduced pressure. For distillation under reduced pressure, it is preferable to use a distillation column or a thin-film distillation apparatus attached to the reaction tank. The pressure in the tank is preferably 3.99 to 0.00133 kPa, and more preferably 1.33 to 0.133 kPa. The temperature in the tank is preferably 20 to 100 ° C, more preferably 20 to 80 ° C, and particularly preferably 40 to 80 ° C in terms of suppressing side reactions.
[0013]
In order to suppress an increase in viscosity due to the progress of distillation under reduced pressure, a new solvent can be added. The solvent to be added is not particularly limited as long as it has a boiling point higher than that of the halogenated fatty acid ester to be distilled off, but can maintain a viscosity of less than 0.5 Pa · s at a tank temperature of 20 to 80 ° C. under reduced pressure conditions. Preferably, it is more preferable to select from ether, hydrocarbon and alcohol (b) described later.
[0014]
Examples of preferred ethers include dipropyl ether, dibutyl ether, dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, propylene glycol dialkyl ether, trialkyl glyceryl ether, polyoxyethylene dimethyl ether , Polyoxyethylene diethyl ether, polyoxyethylene dibutyl ether, polyoxypropylene dialkyl ether, polyoxyethylene-polyoxypropylene copolymerized alcohol dialkyl ether, and polyoxybutylene dialkyl ether.
[0015]
Examples of preferred hydrocarbons include octane, nonane, decane, dodecane, liquid paraffin, methylcyclohexane, toluene, xylene and limonene.
[0016]
[Halogenated fatty acid ester]
The halogenated fatty acid ester of the present invention has the general formula (I)
[0017]
[Chemical formula 2]

[0018]
(In the formula, X is a chlorine atom or a bromine atom, A is a linear or branched alkylene group having 1 to 3 carbon atoms, and R is an alkyl or alkenyl group having 1 to 4 carbon atoms.)
The compound represented by these is preferable. Specifically, methyl chloroacetate, ethyl chloroacetate, propyl chloroacetate, butyl chloroacetate, ethyl bromoacetate, methyl bromoacetate, methyl 2-chloropropionate, ethyl 2-chloropropionate, propyl 2-chloropropionate, Preferred are butyl 2-chloropropionate, methyl 2-bromopropionate, ethyl 2-bromopropionate, propyl 2-bromopropionate, butyl 2-bromopropionate and the like, ethyl chloroacetate, methyl chloroacetate, 2-chloropropion Methyl acid is more preferable, but ethyl chloroacetate is particularly preferable in that it can be easily distilled off under reduced pressure.
[0019]
[Tertiary amine]
The tertiary amine of the present invention preferably has at least one tertiary amino group, and at least one of the substituents on the nitrogen atom of the tertiary amino group is a methyl group or an ethyl group, and 1 Those having no secondary or secondary amino group are more preferred. Among these tertiary amines, the general formula (II), (III) or (IV)
[0020]
[Chemical 3]

[0021]
(Wherein R ¹ Represents a monovalent saturated or unsaturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group or an alicyclic hydrocarbon group, and R ² And R ^Three Each represents a methyl group or an ethyl group, R ^Four CO- is an acyl group having 1 to 30 carbon atoms, R ^Five Represents an alkylene group having 1 to 3 carbon atoms, and R ⁶ And R ⁷ Each represents a methyl group or an ethyl group. . )
In particular, dimethylalkylamine (alkyl group having 1 to 30 carbon atoms), alkanoylaminopropyldimethylamine (alkanoyl group having 2 to 30 carbon atoms), N, N, N ′, N′-tetra Alkyl-1,3-diaminopropane (alkyl group having 1 to 2 carbon atoms) is preferred.
[0022]
Specific examples of these preferred tertiary amines include trimethylamine, ethyldimethylamine, propyldimethylamine, butyldimethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecyldimethylamine, tetradecyldimethylamine, hexadecyldimethyl. Amine, octadecyldimethylamine, eicosanyldimethylamine, docosanyldimethylamine, acetylaminopropyldimethylamine, propanoylaminopropyldimethylamine, butanoylaminopropyldimethylamine, hexanoylaminopropyldimethylamine, octanoylaminopropyldimethylamine Decanoylaminopropyldimethylamine, dodecanoylaminopropyldimethylamine, tetradecanoyl Nopropyldimethylamine, hexadecanoylaminopropyldimethylamine, octadecanoylaminopropyldimethylamine, eicosanoylaminopropyldimethylamine, docosanoylaminopropyldimethylamine, N, N, N ', N'-tetramethyl-1 1,3-diaminopropane and the like.
[0023]
[Transesterification reaction step]
The amount of alcohol (b) charged in the transesterification reaction between betaine ester (A) and alcohol (b) is preferably 1 to 10 equivalents relative to betaine ester (A), and 1 to 2 equivalents reduces unreacted substances. It is more preferable at the point which can be performed. Moreover, when alcohol (b) remains as a solvent in the previous step, the total is preferably within the above range.
[0024]
In the transesterification reaction, the temperature in the tank is preferably 15 to 120 ° C., more preferably 30 to 80 ° C., particularly 40 to 60 ° C. in that the alcohol (a) produced after the reaction can be easily distilled. preferable. Further, the pressure in the tank is preferably 0.00133 to 13.3 kPa, more preferably 0.133 to 5.33 kPa, although it depends on the boiling points of the alcohol (a) and alcohol (b) to be produced.
[0025]
In the transesterification reaction, a generally alkali-stable solvent such as ether or hydrocarbon can be used as necessary. For example, the solvent which can be used at the time of depressurizing distillation of the above-mentioned halogenated fatty acid ester is mentioned.
[0026]
In the transesterification reaction, a basic catalyst is used as a catalyst. As the basic catalyst, a metal alkoxide having excellent compatibility with a reactant is preferable, and an alkali metal alkoxide is more preferable in terms of reactivity at a low temperature. . As the alkali metal alkoxide, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide and the like are preferable, and sodium methoxide and sodium or potassium alkoxide of alcohol (b) are preferable.
[0027]
The amount of the basic catalyst to be added at the time of transesterification is preferably 0.1 to 20 times mol, more preferably 1 to 10 times mol, and particularly preferably 5 to 10 times mol for the betaine ester (A). The basic catalyst is preferably added by dividing dropwise under reduced pressure and stirring.
[0028]
The transesterification reaction is usually completed within 1 to 5 hours after the addition of the basic catalyst. The obtained betaine ester (B) may be subjected to purification such as solvent distillation or crystallization depending on its use, but the reaction-finished product can be used as it is.
[0029]
[Alcohol (b)]
The alcohol (b) used in the present invention is an alcohol having 2 or more carbon atoms excluding the alcohol (a), an aliphatic monohydric alcohol having 5 or more carbon atoms, particularly 5 to 15 carbon atoms, 2 or more carbon atoms, particularly 2 to 2 carbon atoms. 15 aliphatic polyhydric alcohols, fluorinated alcohols having 2 or more carbon atoms, particularly 2 to 28, alicyclic alcohols having 5 or more carbon atoms, particularly 5 to 15 carbon atoms, and aromatic alcohols having 6 or more carbon atoms, particularly 6 to 20 carbon atoms. A heterocyclic alcohol having 5 or more carbon atoms, particularly 5 to 9 carbon atoms is preferred. Furthermore, those having a function that can be imparted to various toiletry products etc. when the alcohol (b) is released alone are preferred, and in particular, the aromatic alcohol (1), which is a blended perfume component, has antibacterial and antifungal properties. Antimicrobial alcohol having (2), moisturizing alcohol having moisture retention (3), physiologically active alcohol having physiological activity and coloring alcohol having coloring property (4), surface modifying property having general surface activity Alcohol (5) is preferable, and aromatic alcohol (1) and antimicrobial alcohol (2) are more preferable.
[0030]
(1) Aromatic alcohols are alcohols used for perfume use described in synthetic perfume (Chemical Industry Daily) and include the following.
[0031]
・ Saturated or unsaturated linear or branched alcohol having 5 to 15 carbon atoms
Green leaf alcohol (cis-3-hexenol), 3-octenol, 9-decenol, geraniol, nerol, citronellol, rosinol, farnesol, hydroxycitronellol and the like.
[0032]
・ C6-C12 aromatic alcohol
Benzyl alcohol, β-phenylethyl alcohol, cinnamic alcohol, γ-phenylpropyl alcohol, anise alcohol, phenoxyethyl alcohol, styryl alcohol, 3-methyl-5-phenylpentanol, 2,2-dimethyl-3- (3 -Methylphenyl) -propanol and the like.
[0033]
・ Saturated or unsaturated cyclic alcohol having 8 to 15 carbon atoms
2,4-dimethyl-3-cyclohexene-1-methanol, 4-isopropylcyclohexylmethanol, 1- (4-isopropylcyclohexyl) ethanol, p-tert-butylcyclohexanol, o-tert-butylcyclohexanol, L-menthol 1- (2-t-butylcyclohexyloxy) -2-butanol, pentamethylcyclohexylpropanol, 1- (2,2,6-trimethylcyclohexyl) -3-hexanol, santalol, vetiverol and the like.
[0034]
(2) Antimicrobial alcohol is alcohol used for antibacterial and antifungal purposes described in the Japanese Antibacterial and Antifungal Dictionary (published by the Japanese Society for Antibacterial and Antifungal Society), and includes the following.
[0035]
・ C3-C15 fatty acid polyhydric alcohol
Glycerol monolaurate, tri (hydroxymethyl) nitromethane, 2-bromo-2-nitropropane-1,3-diol, etc.
[0036]
・ C7-9 heterocyclic alcohol
1,3-bis (hydroxymethyl) -5,5′-dimethylhydantoin, hexahydro-1,3,5-tris (hydroxyethyl) -S-triazine and the like.
[0037]
(3) Moisturizing alcohol is an alcohol that generally has a moisturizing effect, and includes the following.
[0038]
・ C2-C6 aliphatic polyhydric alcohol
Glycerin, propylene glycol, ethylene glycol, pentaerythritol, glucose and the like.
[0039]
(4) The physiologically active alcohol and the coloring alcohol are vitamins having a hydroxyl group, adrenocorticotropic hormone, pheromone, carotenoid and the like, and the following are preferable.
[0040]
・ Unsaturated linear or cyclic monovalent or polyhydric alcohol having 16 to 40 carbon atoms
Vitamin A ₁ , Vitamin A ₂ , Riboflavin, L-ascorbic acid, vitamin D ₂ , Vitamin D _Three , Vitamin D _Four Corticosterone, dehydrocorticosterone, deoxycorticosterone, bombycol, violaxanthin, cryptoxanthin, zeaxanthin, lutein, rubixanthine and the like.
[0041]
・ C20 aromatic alcohol
Kinin, quinidine, etc.
[0042]
(5) Examples of the surface-modifying alcohol include the following.
[0043]
. Polyalkylene alkyl ether represented by the formula (V)
R ¹¹ -O- (R ¹² O) _p -H (V)
(Wherein R ¹¹ Is an alkyl or alkenyl group having 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms, R ¹² Is a C2-C3 linear or branched alkylene group, p is 1-20, preferably 1-10. )
Specifically, ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyoxyethylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxyethylene monooleyl ether, polyoxypropylene monoalkyl ether, polyoxyethylene monoalkyl ether Oxyethylene-polyoxypropylene copolymer alcohol monoalkyl ether, polyoxybutylene monoalkyl ether, and the like.
[0044]
・ Glyceryl ether represented by the formula (VI)
R ¹³ -O-CH ₂ -CH (OR ¹⁴ ) -CH ₂ -O-R ¹⁵ (VI)
[Wherein R ¹³ , R ¹⁴ And R ¹⁵ Are the same or different, a hydrogen atom, or formula (VII)
R ¹¹ -O- (R ¹² O) _q − (VII)
(R ¹¹ And R ¹² Represents the same meaning as described above, and q represents a number of 0 to 20. )
R represents a group represented by R ¹³ , R ¹⁴ , R ¹⁵ At least one of them is a hydrogen atom, and all do not become a hydrogen atom at the same time. ]
Specifically, monoalkyl glyceryl ether, dialkyl glyceryl ether, methyltriethylene glyceryl ether, etc.
・ Alkyl glycosides having an alkyl chain of 1 to 18 carbon atoms
Specifically, α-methyl glycoside, β-dodecyl glycoside and the like.
[0045]
・ Fluorine-containing alcohol represented by formula (VIII)
R ^f -(CH ₂ ) _n -OH (VIII)
(Wherein R ^f Represents a fluoroalkyl group in which at least one hydrogen atom of a linear or branched alkyl group having 1 to 20 carbon atoms is substituted with a fluorine atom, and n represents an integer of 1 to 8. )
Specific examples include 2,2,3,3,3-pentafluoropropanol, 2- (perfluorooctyl) ethanol, 2- (perfluorodecyl) ethanol, 6- (perfluoroethyl) hexanol, 6- (perfluoro Butyl) hexanol, 6- (perfluorohexyl) hexanol, 6- (perfluorooctyl) hexanol, 6- (perfluoroisopropyl) hexanol, 4,4,4-trifluorobutanol, 2,2,3,4,4 , 4-Hexafluorobutanol, 2,2,3,3-tetrafluoropropanol, 1H, 1H, 5H-octafluoropentanol, 1H, 1H, 7H-dodecafluoroheptanol, 1H, 1H, 9H-hexadecafluoro Nonanol, 2- (perfluoro-3-methylbutyl) ethanol, 2- (perfluoro-5-methylhexyl) ethanol, 2- (perfluoro-7-methyloctyl) ethanol, 2- (perfluoro -9-methyldodecyl) ethanol, 6- (perfluoro-1-methylethyl) hexanol, 2- (perfluoro-3-methylbutyl) hexanol, 6- (perfluoro-5-methylhexyl) hexanol, 6- (per Fluoro-7-methyloctyl) hexanol, 4,4,4-trifluoro-2-buten-1-ol, 1H, 1H, 2H, 2H, 3H, 3H-perfluorononanol and the like.
[0046]
【Example】
Parts and% in the examples are based on weight unless otherwise specified.
[0047]
Example 1: Preparation of N, N-dimethyl-N-geranyloxycarbonylmethyl-N- (3- (octadecanoylamino) propyl) ammonium chloride
N, N-dimethyl-N'-octadecanoyl-1,3-diaminopropane 3.69kg (10mol) and 29.5L of 99.5% ethanol (2.5kg) were charged into the reaction vessel, heated and dissolved in a dry nitrogen atmosphere at 45 ° C. The mixture was kept warm and stirred, and 1.35 kg (11 mol) of ethyl chloroacetate was added thereto at a dropping rate of 60 mL / min, followed by stirring at a temperature of 45 ± 3 ° C. for 10 hours. Of the reaction mixture ¹ After measuring the H-NMR spectrum (FT, 200 MHz) and confirming that the absorption peak derived from the raw material amine has disappeared, the inside of the tank was depressurized and the dry nitrogen was 0.2 m. ^Three The remaining ethyl chloroacetate and ethanol were distilled off under reduced pressure while blowing with / h. When the distillate was collected up to 2.3L in the fraction receiver, dry nitrogen was introduced into the tank and the viscosity of the reaction mixture in the tank was measured at normal pressure, and it was 485 mPa · s. A tendency was observed, and the residual amount of ethyl chloroacetate in the reaction product was 1.6% as measured by gas chromatography. At this point, 3.1 kg (20 mol) of geraniol was charged and stirred at 45 ° C. for 10 minutes. After confirming that the viscosity of the reaction product was 250 mPa · s, the contents in the tank were transferred to a thin-film distillation apparatus (Smith type). . The wall temperature of the distiller was set to 49 ° C., and the pressure was set to 0.133 kPa. When the residual amount of ethyl chloroacetate in the mixture of the intermediate betaine ester and geraniol remaining in the distiller was measured using gas chromatography, it was below the lower limit of detection (15 mg / kg). The obtained pale yellow oily mixture was transferred to a reaction tank, and 408 mL of 28% sodium methoxide methanol solution was added 5 times at 40 minute intervals at a tank temperature of 43 ± 2 ° C and a tank pressure of 1.33 to 2.67 kPa. A transesterification reaction was carried out. The total effective amount of sodium methoxide in the reaction product was 54 g (1 mol). 40 minutes after the fifth addition of sodium methoxide ¹ When the H-NMR spectrum was measured, the absorption peak derived from ethyl ester disappeared, and N, N-dimethyl-N-geranyloxycarbonylmethyl-N- (3- (octadecanoyl chloride) containing 18% geraniol was found. 7.31 kg (10 mol; yield: 100%) of amino) propyl) ammonium was obtained as a light brown liquid having a viscosity of 210 mPa · s at 40 ° C. (light brown waxy substance at 25 ° C.). The amounts of ethyl chloroacetate and geranyl chloroacetate contained in this product were both less than 10 mg / kg by GC and GC / MASS determination.
[0048]
Example 2: Preparation of 1,3-bis (N, N-dimethyl-N-geranyloxycarbonylmethylammonium chloride) propane
Charge N, N, N ', N'-tetramethyl-1,3-diaminopropane 2.6 kg (20 mol) and 99.5% ethanol 5 L (4 kg) in a reaction tank, heat and dissolve in a dry nitrogen atmosphere, and keep at 45 ° C. -While stirring, 2.69 kg (22 mol) of ethyl chloroacetate was added thereto at a dropping rate of 60 L / min, and the mixture was stirred for 5 hours at 45 ± 3 ° C in the tank. Of the reaction mixture ¹ After measuring the H-NMR spectrum (FT, 200 MHz) and confirming that the absorption peak derived from the raw material amine has disappeared, the inside of the tank was depressurized and the dry nitrogen was 0.2 m. ^Three The remaining ethyl chloroacetate and ethanol were distilled off under reduced pressure while blowing with / h. When the distillate was collected up to 5 L in the fraction receiver, dry nitrogen was introduced into the tank and the viscosity of the reaction mixture in the tank was measured at normal pressure, and it was 630 mPa · s. The amount of ethyl chloroacetate in the reaction product was measured by gas chromatography and found to be 2.8%. At this point, 7.7 kg (50 mol) of geraniol was charged and stirred at 45 ° C. for 10 minutes. After confirming that the viscosity of the reaction product was 490 mPa · s, the contents in the tank were transferred to a thin-film distillation apparatus (Smith type). . The wall temperature of the still was set to 49 ° C. and the pressure was set to 0.133 kPa, and the distillation under reduced pressure was further performed for 10 hours. When the residual amount of ethyl chloroacetate in the mixture of the intermediate betaine ester and geraniol remaining in the distiller was measured using gas chromatography, it was below the lower limit of detection (15 mg / kg). The obtained pale yellow oily mixture was transferred to the reaction vessel and stabilized at a temperature of 43 ± 2 ° C and a pressure of 1.33 to 2.66 kPa. Then, 81.6 mL of 28% sodium methoxide methanol solution was added every 40 minutes. Was added 5 times in total for transesterification. The total effective amount of sodium methoxide in the reaction product was 108 g (2 mol). 40 minutes after the fifth addition of sodium methoxide ¹ When the H-NMR spectrum was measured, the absorption peak derived from the ethyl ester disappeared, and 1,3-bis (N, N-dimethyl-N-geranyloxycarbonylmethylammonium chloride) propane containing 11.5% geraniol was detected. As a light brown liquid having a viscosity of 490 mPa · s at 40 ° C. (light brown waxy substance at 25 ° C.), 13.4 kg (20 mol; yield: 100%) was obtained. The amounts of ethyl chloroacetate and geranyl chloroacetate contained in this product were both less than 10 mg / kg by GC / MASS determination.
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Example 3: Preparation of N, N-dimethyl-N-menthyloxycarbonylmethyl-N- (3- (octadecanoylamino) propyl) ammonium chloride
Charge N, N-dimethyl-N'-octadecanoyl-1,3-diaminopropane 3.69kg (10mol) and 2L (2.5kg) 99.5% ethanol in a reaction tank, heat and dissolve in dry nitrogen atmosphere at 45 ° C The mixture was kept warm and stirred, and 1.35 kg (11 mol) of ethyl chloroacetate was added thereto at a dropping rate of 60 mL / min, and stirred at a temperature in the tank of 45 ± 3 ° C. for 10 hours. Of the reaction mixture ¹ After measuring the H-NMR spectrum (FT, 200 MHz) and confirming that the absorption peak derived from the raw material amine has disappeared, the inside of the tank was depressurized and the dry nitrogen was 0.2 m. ^Three The remaining ethyl chloroacetate and ethanol were distilled off under reduced pressure while blowing with / h. When the distillate was collected up to 2.3 L in the fraction receiver, dry nitrogen was introduced into the tank and the viscosity of the reaction mixture in the tank was measured at normal pressure, and it was 500 mPa · s, indicating an increase in viscosity. A tendency was observed, and the residual amount of ethyl chloroacetate in the reaction product was measured by gas chromatography and found to be 1.5%. At this point, 3.14 kg (20 mol) of menthol was charged and stirred for 10 minutes at 45 ° C. After confirming that the viscosity of the reaction product was 250 mPa · s, the contents in the tank were transferred to a thin-film distillation apparatus (Smith type). . The wall temperature of the distiller was set to 49 ° C. and the pressure was set to 0.133 kPa, and distillation under reduced pressure was further performed for 8 hours. When the residual amount of ethyl chloroacetate in the mixture of the intermediate betaine ester and menthol remaining in the distiller was measured using gas chromatography, it was below the lower limit of detection (15 mg / kg). The obtained pale yellow oily mixture was transferred to a reaction tank, 10 L of limonene was added to the reaction tank, and 81.6 mL of 28% sodium methoxide methanol solution was added at a tank temperature of 70 ± 2 ° C. and a tank pressure of 1.33 to 2.67 kPa. A total of 5 additions were made at 40 minute intervals to conduct the transesterification reaction. The total effective amount of sodium methoxide in the reaction product was 108 g (2 mol). 40 minutes after the fifth addition of sodium methoxide ¹ When the H-NMR spectrum was measured, the absorption peak derived from ethyl ester disappeared. In the tank, 100 L of acetone was added at 50 ° C. ± 2 ° C., and stirred at 50 ° C. ± 2 ° C. for 1 hour to make a uniform solution. The reaction solution was cooled to room temperature and crystallized to remove most of menthol and limonene. The crystals were dried under reduced pressure, and 4.15 kg (7.5 mol) of N, N-dimethyl-N-menthyloxycarbonylmethyl-N- (3- (octadecanoylamino) propyl) ammonium chloride containing 18% menthol as yellow crystals. Yield 75%). The amounts of ethyl chloroacetate and menthyl chloroacetate contained in this product were both less than 10 mg / kg by GC and GC / MASS determination.
[0050]
Example 4: Preparation of N, N, N-trimethyl-N-geranyloxycarbonylmethylammonium chloride
The reaction vessel was charged with 400 g of 99.5% ethanol and 42 g (0.34 mol) of ethyl chloroacetate and cooled to 0 ° C. 90 g (1.52 mol) of trimethylamine was introduced from a cylinder and stirred at 0 ° C. for 10 hours. The reaction mixture was heated to 45 ° C., and trimethylamine, ethyl chloroacetate and ethanol remaining under reduced pressure of 1.33 kPa were distilled off under reduced pressure. 79 g (0.5 mol) of geraniol was charged and stirred at 45 ° C. for 10 minutes. After confirming that the viscosity of the reaction product was 250 mPa · s, the contents in the tank were transferred to a thin-film distillation apparatus (Smith type). The wall temperature of the distiller was set to 49 ° C. and the pressure was set to 0.133 kPa, and distillation under reduced pressure was further performed for 8 hours. When the residual amount of ethyl chloroacetate in the mixture of the intermediate betaine ester and geraniol remaining in the distiller was measured using gas chromatography, it was below the lower limit of detection (15 mg / kg). The obtained pale yellow oily mixture was transferred to a reaction tank, and at a tank temperature of 43 ± 2 ° C. and a tank pressure of 1.33 to 2.67 kPa, 13 g (0.07 mol) of 28% sodium methoxide methanol solution was added at intervals of 40 minutes. A total of 5 times was added to conduct transesterification. The total effective amount of sodium methoxide in the reaction product was 18.4 g (0.34 mol). 40 minutes after the fifth addition of sodium methoxide ¹ When the H-NMR spectrum was measured, the absorption peak derived from the ethyl ester disappeared, and N, N, N-trimethyl-N-geranyloxycarbonylmethylammonium chloride containing about 18% geraniol had a viscosity of 210 mPa at 40 ° C. -127 g (0.34 mol; yield 100%) was obtained as a light brown liquid of s (light brown waxy substance at 25 ° C.). The amounts of ethyl chloroacetate and geranyl chloroacetate contained in this product were both less than 10 mg / kg by GC and GC / MASS determination.
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Example 5: Preparation of N, N-dimethyl-N-dodecyl-N-geranyloxycarbonylmethylammonium chloride
The same procedure as in Example 4 was conducted except that 66 g (0.31 mol) of dodecyldimethylamine was used instead of 90 g (1.52 mol) of trimethylamine and the reaction was performed at 45 ° C. 162 g (0.31 mol; yield 100%) of N, N-dimethyl-N-dodecyl-N-geranyloxycarbonylmethylammonium chloride containing about 12% of geraniol was obtained as a light brown wax. The amounts of ethyl chloroacetate and geranyl chloroacetate contained in this product were both less than 10 mg / kg by GC and GC / MASS determination.
[0052]
【The invention's effect】
According to the present invention, it is possible to efficiently produce high-quality, low-cost, and betaine esters such as high-molecular-weight alcohols, polyhydric alcohols, and alcohols that easily cause side reactions such as dehydration and rearrangement, which have been difficult to produce industrially. .

Claims (2)

A halogenated fatty acid ester of a saturated or unsaturated monohydric alcohol having 1 to 4 carbon atoms (hereinafter referred to as alcohol (a)) represented by the following general formula (I) and the following general formulas (II) to (IV) And a tertiary amine to be reacted at 0 to 100 ° C., and then unreacted halogenated fatty acid ester is distilled off under reduced pressure to obtain a betaine ester of alcohol (a) (hereinafter referred to as betaine ester (A)). And betaine ester (A) and green leaf alcohol (cis-3-hexenol), 3-octenol, 9-decenol, geraniol, nerol, citronellol, rosinol, farnesol, hydroxycitronellol, 2,4-dimethyl-3-cyclohexene- 1-methanol, 4-isopropylcyclohexylmethanol, 1- (4-isopropylcyclohexyl) ethanol, p-tert-butylcyclohexa , O-tert-butylcyclohexanol, L-menthol, 1- (2-t-butylcyclohexyloxy) -2-butanol, pentamethylcyclohexylpropanol, 1- (2,2,6-trimethylcyclohexyl) -3 A method for producing a betaine ester comprising a step of transesterifying an alcohol selected from hexanol, santalol and vetiverol (hereinafter referred to as alcohol (b)) in the presence of an alkali metal alkoxide to obtain a betaine ester of alcohol (b) .

(In the formula, X is a chlorine atom or a bromine atom, A is a linear or branched alkylene group having 1 to 3 carbon atoms, and R is an alkyl or alkenyl group having 1 to 4 carbon atoms.)

Wherein R ¹ represents a monovalent saturated or unsaturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group or an alicyclic hydrocarbon group, and R ² and R ³ are each a methyl group Or R ⁴ represents an alkyl group having 1 to 29 carbon atoms , R ⁵ represents an alkylene group having 1 to 3 carbon atoms, and R ⁶ and R ⁷ each represent a methyl group or an ethyl group.   The method for producing a betaine ester according to claim 1, wherein the unreacted halogenated fatty acid ester is distilled off under reduced pressure in the presence of the alcohol (b).