JP5358802B2 - 新規な希少糖脂肪酸ジエステルの製造方法 - Google Patents
新規な希少糖脂肪酸ジエステルの製造方法 Download PDFInfo
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- JP5358802B2 JP5358802B2 JP2007069527A JP2007069527A JP5358802B2 JP 5358802 B2 JP5358802 B2 JP 5358802B2 JP 2007069527 A JP2007069527 A JP 2007069527A JP 2007069527 A JP2007069527 A JP 2007069527A JP 5358802 B2 JP5358802 B2 JP 5358802B2
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- psicose
- reaction
- rare sugar
- acid diester
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Description
また、D−プシコースの有効エネルギー価はほぼゼロであることも報告されている(非特許文献2)。
さらに、より実用的な応用研究のため、プシコースのレチノイン酸エステル(特許文献1)、D−アロース−6−オクタン酸エステル、D−アロース−6−デカン酸エステルおよび、D−アロース−6−ドデカン酸エステル(特許文献2)などの希少糖のエステルがせいぞうされているが、希少糖の水酸基を選択的に直鎖脂肪酸ジエステルに変換すれば、膜親和性あるいは膜透過性が増加し、希少糖より生理活性が増加することが期待できる。
希少糖の脂肪酸ジエステルは、膜親和性あるいは膜透過性が増加し、希少糖より生理活性が向上し、その結果、希少糖の実用的な応用研究に役立つことが期待できる。
また、本発明は、新規な希少糖の脂肪酸ジエステルを提供することを目的とする。
(1)下記の反応式1
で表される、希少糖に属するD−プシコース(I)をオクタン酸ビニルエステル、デカン酸ビニルエステルおよびドデカン酸ビニルエステルからなる群から選ばれる一の脂肪酸ビニルエステルからなる脂肪酸アシル供与体(II)と、リパーゼNovozyme435(ノボザイム社製)の存在下溶媒としてのアセトニトリル中で接触させることによって希少糖残基がD−プシコース残基である、D−プシコース脂肪酸ジエステル(III)を製造することを特徴とする希少糖脂肪酸ジエステルの製造方法。
また、本発明は、希少糖の水酸基を選択的に直鎖脂肪酸ジエステルに変換する方法を提供することができる。
プシコース、D− タガトース、D− ソルボース、L− フラクトース、L− プシコース、L− タガトース、L− ソルボースが挙げられる。
脂肪酸又は脂肪酸の低級アルコールエステルも使用できるが、反応時間が長くなり、収率も低くなる。脂肪酸又は脂肪酸の低級アルコールエステルである。脂肪酸は、炭素数6〜22の飽和もしくは不飽和で直鎖もしくは分岐鎖脂肪酸であり、このような脂肪酸であれば、水酸基,カルボニル基,フェニル基等で置換されたものでも良い。具体的には、脂肪酸としてカプロン酸,ソルビン酸,カプリル酸,カプリン酸,ラウリン酸,ミリスチン酸,パルミトレイン酸,パルミチン酸,ステアリン酸,イソステアリン酸,オレイン酸,リノール酸,リノレン酸,ペンタデカン酸,エイコサン酸,ドコサン酸,ドコセン酸,アラキドン酸,リシノレイン酸,ジヒドロキシステアリン酸等を使用することができる。
(1)反応条件
リパーゼについては、amano-PS(Pseudomonas cepacia), amino-AK (Pseudomonas fluorescence), PPL(Porcine pancreas)およびNovozyme435 (Candida Antarctica)を検討し、溶媒については、ヘキサン、アセトン、アセトニトリルおよびピリジンを検討した結果、D−プシコースのアシル化は、固定化リパーゼNovozyme435とオクタン酸ビニルを用いてTHF中、45℃、2日間反応させると収率良く進行することが分かった。
同様に、デカン酸ビニルおよびドデカン酸ビニルを用いるとジアシル化反応が進行し、相当するD−プシコース直鎖脂肪酸ジエステルが得られた。
酵素反応後、反応混合物をセライトろ過し、リパーゼを取り除いた。ろ液を濃縮後、ヘキサン−酢酸エチル混合液で洗浄し、過剰の脂肪酸ビニルエステルを取り除いた。この後、通常のシリカゲルのカラムクロマトグラフィにより、D−プシコース脂肪酸ジエステルを精製した。大量合成の場合、ヘキサン−酢酸エチル混合液あるいはアセトンからの再結晶も有効である。
1H-NMRおよび13C-NMRより、D−プシコース脂肪酸ジエステルは、1,6位の水酸基がエステル化されていることがわかった。また、糖部分は、5員環構造のフラノース型であることがわかった。また、アノマーの比は、α−アノマーとβ−アノマーが約1:1であることが1H-NMR測定により明らかになった。D−プシコース直鎖脂肪酸ジエステルのα−アノマーでは、1,6位の2個の脂肪酸部分が立体的にシスの立体配置を取ることになり、β−アノマーと比べその物理化学的性質が大きく変わることが予想される。また、α−アノマーは生体の二分子膜に類似した構造であるので、生理活性の向上が大いに期待できる。
で表される。
n=6;1,6−ジオクタノイル−D−プシコース
n=8;1,6−ジデカノイル−D−プシコース
n=10;1,6−ジドデカノイル−D−プシコース
D−プシコース(80mg)のアセトニトリル溶液(8 ml)にオクタン酸ビニル(0.26ml)とNovozyme435(80mg)を加え、45℃、250rpmで反応させた。TLC分析により、1日間で反応が終了していることを確認後、セライトを用いて反応混合物をろ過し、メタノールで3回洗浄した。ろ液を減圧下濃縮した。残留物をヘキサン−酢酸エチル混合液(0.5ml)で洗浄後、シリカゲルのカラムクロマトグラフィで精製し、D−プシコース1,6−オクタン酸ジエステル(159mg、83%)を得た。
また、洗浄した反応物を一晩放置すると結晶化するので、ヘキサン−酢酸エチル混合液あるいはアセトンより再結晶できる。
mp 58-61 ℃;[α]D +10.0°(c1.0, CH3OH); IRnmax (KBr)cm-1: 3421, 2956, 1743, 1704, 1197, 1112, 964, 613;13C-NMR(100MHz, CD3OD)δ 14.4, 23.7, 26.0, 30.1, 30.2, 32.9, 34.9, 65.1(aC-6), 65.7(bC-6), 66.0(aC-1), 66.9(bC-1), 72.5(aC-3,4), 73.3 (bC-4), 76.2(bC-3), 81.5(aC-5), 81.7(bC-5), 103.2(aC-2), 106.0(bC-2), 174.7(6-bCO), 175.1(6-aCO), 175.39(1-aCO), 175.43(1-bCO).
D−プシコース(80mg)のアセトニトリル溶液(8ml)にデカン酸ビニル(0.30ml)とNovozyme435(80mg)を加え、45℃、250rpmで反応させた。TLC分析により、1日間で反応が終了していることを確認後、セライトを用いて反応混合物をろ過し、メタノールで3回洗浄した。ろ液を減圧下濃縮した。残留物をヘキサン−酢酸エチル混合液(0.5ml)で洗浄後、シリカゲルのカラムクロマトグラフィで精製し、D−アロース−6−デカン酸エステル(186mg、86%)を得た。
また、洗浄した反応物を一晩放置すると結晶化するので、ヘキサン−酢酸エチル混合液あるいはアセトンより再結晶できる。
mp 71-74 ℃;[α]D +4.0°(c1.0, CH3OH); IRnmax (KBr)cm-1: 3418, 2921, 2851, 1745, 1703, 1469, 1395, 1255, 1195, 1114, 965, 721;13C-NMR (100MHz, CD3OD)δ 14.4, 23.7, 26.0, 30.1, 30.2, 32.9, 34.9, 65.1(aC-6), 65.7(bC-6), 66.0(aC-1), 66.9(bC-1), 72.4(aC-4), 72.5(aC-3)73.3 (bC-4), 76.2(bC-3), 81.5(aC-5), 81.7(bC-5), 103.1(aC-2), 106.0(bC-2), 174.7(6-a, b CO), 175.1(1-aCO), 175.4 (1-bCO).
D−プシコース(80mg)のアセトニトリル溶液(8ml)にドデカン酸ビニル(0.35ml)とNovozyme435(80mg)を加え、45℃、250rpmで反応させた。TLC分析により、1日間で反応が終了していることを確認後、セライトを用いて反応混合物をろ過し、メタノールで3回洗浄した。ろ液を減圧下濃縮した。残留物をヘキサン−酢酸エチル混合液(0.5ml)で洗浄後、シリカゲルのカラムクロマトグラフィで精製し、D−アロース−6−ドデカン酸エステル(218mg、90%)を得た。
また、洗浄した反応物を一晩放置すると結晶化するので、ヘキサン−酢酸エチル混合液あるいはアセトンより再結晶できる。
mp 80-82 ℃; [α]D +2.0°(c1.0, CH3OH); IRnmax (KBr)cm-1: 3336, 2918, 2850, 2359, 1725, 1466, 1183, 1083, 949, 861, 720;13C-NMR(100MHz, CD3OD)δ 14.4, 23.7, 26.0, 30.1, 30.2, 32.9, 34.9, 65.1(aC-6), 65.7(bC-6), 66.0(aC-1), 66.9(bC-1), 72.5(aC-3,4), 73.3 (bC-4), 76.2(bC-3), 81.6(aC-5), 81.7(bC-5), 103.2(aC-2), 106.0(bC-2), 174.7(6-bCO), 175.1(6-aCO), 175.39(1-aCO), 175.43(1-bCO).
Claims (1)
- 下記の反応式1
で表される、希少糖に属するD−プシコース(I)をオクタン酸ビニルエステル、デカン酸ビニルエステルおよびドデカン酸ビニルエステルからなる群から選ばれる一の脂肪酸ビニルエステルからなる脂肪酸アシル供与体(II)と、リパーゼNovozyme435(ノボザイム社製)の存在下溶媒としてのアセトニトリル中で接触させることによって希少糖残基がD−プシコース残基である、D−プシコース脂肪酸ジエステル(III)を製造することを特徴とする希少糖脂肪酸ジエステルの製造方法。
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JPS58110519A (ja) * | 1981-12-25 | 1983-07-01 | Mitsui Toatsu Chem Inc | 鼓脹症予防剤、又は治療剤 |
JPH03168091A (ja) * | 1989-11-27 | 1991-07-19 | Lion Corp | 糖脂肪酸エステルの製造方法 |
JPH03168093A (ja) * | 1989-11-27 | 1991-07-19 | Lion Corp | 糖脂肪酸エステルの精製方法 |
JPH06293789A (ja) * | 1993-04-08 | 1994-10-21 | Teijin Ltd | 多価不飽和脂肪酸類配糖体およびその製造方法 |
JPH09168395A (ja) * | 1995-12-21 | 1997-06-30 | Lion Corp | 糖脂肪酸エステルの製造方法 |
JPH09224694A (ja) * | 1996-02-22 | 1997-09-02 | Lion Corp | 糖脂肪酸エステルの製造方法 |
JP4535238B2 (ja) * | 2004-03-17 | 2010-09-01 | 国立大学法人 香川大学 | プシコースのレチノイン酸エステル及びその製造方法 |
JP4644433B2 (ja) * | 2004-03-19 | 2011-03-02 | 合同会社希少糖生産技術研究所 | 新規なd−アロース脂肪酸エステルの製造方法 |
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