JPS61251695A - Purification of saccharide fatty acid ester - Google Patents
Purification of saccharide fatty acid esterInfo
- Publication number
- JPS61251695A JPS61251695A JP60094446A JP9444685A JPS61251695A JP S61251695 A JPS61251695 A JP S61251695A JP 60094446 A JP60094446 A JP 60094446A JP 9444685 A JP9444685 A JP 9444685A JP S61251695 A JPS61251695 A JP S61251695A
- Authority
- JP
- Japan
- Prior art keywords
- fatty acid
- reaction
- acid ester
- water
- saccharide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 saccharide fatty acid ester Chemical class 0.000 title claims abstract description 52
- 239000000194 fatty acid Substances 0.000 title claims abstract description 47
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 46
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 46
- 238000000746 purification Methods 0.000 title description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 12
- 235000000346 sugar Nutrition 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 5
- 150000002148 esters Chemical class 0.000 abstract description 4
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 2
- WTBAHSZERDXKKZ-UHFFFAOYSA-N octadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCC(Cl)=O WTBAHSZERDXKKZ-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001720 carbohydrates Chemical class 0.000 abstract 2
- 239000011541 reaction mixture Substances 0.000 abstract 2
- 239000002246 antineoplastic agent Substances 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 235000013305 food Nutrition 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 229930006000 Sucrose Natural products 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000005720 sucrose Substances 0.000 description 5
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 150000008163 sugars Chemical class 0.000 description 4
- 150000005690 diesters Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- HVHPUSJJNKGXHK-YJLYGGOZSA-N (2s,4s,5r)-1-(4-tert-butylbenzoyl)-4-cyano-2-(2-methylpropyl)-5-(1,3-thiazol-2-yl)pyrrolidine-2-carboxylic acid Chemical compound N1([C@H]([C@@H](C#N)C[C@@]1(CC(C)C)C(O)=O)C=1SC=CN=1)C(=O)C1=CC=C(C(C)(C)C)C=C1 HVHPUSJJNKGXHK-YJLYGGOZSA-N 0.000 description 2
- FXHXHEBILRVVHR-NREQDYHMSA-N CCCCCCCCCCCCCCCCCC(O)=O.O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@H]1[C@H](O)[C@@H](O)C(O)O[C@@H]1CO Chemical compound CCCCCCCCCCCCCCCCCC(O)=O.O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@H]1[C@H](O)[C@@H](O)C(O)O[C@@H]1CO FXHXHEBILRVVHR-NREQDYHMSA-N 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 150000004043 trisaccharides Chemical class 0.000 description 2
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 1
- FEWLNYSYJNLUOO-UHFFFAOYSA-N 1-Piperidinecarboxaldehyde Chemical compound O=CN1CCCCC1 FEWLNYSYJNLUOO-UHFFFAOYSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PZPXDAEZSA-N 4β-mannobiose Chemical compound O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-PZPXDAEZSA-N 0.000 description 1
- PVXPPJIGRGXGCY-DJHAAKORSA-N 6-O-alpha-D-glucopyranosyl-alpha-D-fructofuranose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@](O)(CO)O1 PVXPPJIGRGXGCY-DJHAAKORSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- WSVLPVUVIUVCRA-KPKNDVKVSA-N Alpha-lactose monohydrate Chemical compound O.O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O WSVLPVUVIUVCRA-KPKNDVKVSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- DKXNBNKWCZZMJT-UHFFFAOYSA-N O4-alpha-D-Mannopyranosyl-D-mannose Natural products O=CC(O)C(O)C(C(O)CO)OC1OC(CO)C(O)C(O)C1O DKXNBNKWCZZMJT-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- MUPFEKGTMRGPLJ-RMMQSMQOSA-N Raffinose Natural products O(C[C@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@@H](O[C@@]2(CO)[C@H](O)[C@@H](O)[C@@H](CO)O2)O1)[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 MUPFEKGTMRGPLJ-RMMQSMQOSA-N 0.000 description 1
- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 description 1
- MUPFEKGTMRGPLJ-UHFFFAOYSA-N UNPD196149 Natural products OC1C(O)C(CO)OC1(CO)OC1C(O)C(O)C(O)C(COC2C(C(O)C(O)C(CO)O2)O)O1 MUPFEKGTMRGPLJ-UHFFFAOYSA-N 0.000 description 1
- ZPVGIKNDGJGLCO-VGAMQAOUSA-N [(2s,3r,4s,5s,6r)-2-[(2s,3s,4s,5r)-3,4-dihydroxy-2,5-bis(hydroxymethyl)oxolan-2-yl]-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)O[C@@]1([C@]2(CO)[C@H]([C@H](O)[C@@H](CO)O2)O)O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O ZPVGIKNDGJGLCO-VGAMQAOUSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- HDTRYLNUVZCQOY-LIZSDCNHSA-N alpha,alpha-trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000003084 food emulsifier Nutrition 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- ARBOVOVUTSQWSS-UHFFFAOYSA-N hexadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCC(Cl)=O ARBOVOVUTSQWSS-UHFFFAOYSA-N 0.000 description 1
- 230000003308 immunostimulating effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N n-hexadecanoic acid Natural products CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- MUPFEKGTMRGPLJ-ZQSKZDJDSA-N raffinose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O2)O)O1 MUPFEKGTMRGPLJ-ZQSKZDJDSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
Abstract
Description
【発明の詳細な説明】
本発明は糖脂肪酸エステルの精製法に関するものである
。糖脂肪酸エステルのなかで、ショ糖脂肪酸エステルは
優れた食品用乳化剤として、使用されている。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for purifying sugar fatty acid esters. Among sugar fatty acid esters, sucrose fatty acid esters are used as excellent food emulsifiers.
また、ショ糖脂肪酸エステルや、その他の糖脂肪酸エス
テルには、抗腫瘍性、免疫賦活作用、抗菌性、植物生長
抑制作用を示すものがあることが最近の研究で明らかに
なってきた。Furthermore, recent research has revealed that some sucrose fatty acid esters and other sugar fatty acid esters exhibit antitumor, immunostimulating, antibacterial, and plant growth inhibiting effects.
糖脂肪酸エステルは、糖と脂肪酸低級アルコールエステ
ルによるエステル交換反応、糖とトリグリセライドによ
るエステル交換反応、糖と脂肪酸ハライドまたは脂肪酸
熱°水物によるアシル化反応。Sugar fatty acid esters are produced through transesterification reactions between sugars and fatty acid lower alcohol esters, transesterification reactions between sugars and triglycerides, and acylation reactions between sugars and fatty acid halides or hot fatty acid hydrates.
酵素反応により合成される。Synthesized by enzymatic reaction.
糖と脂肪酸ハライドによるアシル化反応はピリジン、ピ
ロリドン、ピペリジン、モルホリン等の含窒素化合物を
反応溶媒として用いる。その場合の精製法は、（１）反
応溶液より高温減圧下に溶媒を除去したのち、残液より
糖脂肪酸エステルを抽出する方法、（２）反応容器に直
接水と有機溶媒を加え未反応側を水層に、糖脂肪酸エス
テルを有機溶媒層に分配させる方法、（３）反応溶液に
多量の水を加え水に不溶の糖脂肪酸エステルのポリエス
テルを沈澱物として得る方法が報告されている。In the acylation reaction between sugar and fatty acid halide, a nitrogen-containing compound such as pyridine, pyrrolidone, piperidine, or morpholine is used as a reaction solvent. In that case, the purification methods are (1) removing the solvent from the reaction solution under high temperature and reduced pressure, and then extracting the sugar fatty acid ester from the residual liquid; (2) adding water and an organic solvent directly to the reaction vessel and removing the unreacted Two methods have been reported: (3) a method in which a large amount of water is added to the reaction solution to obtain a polyester of a sugar-fatty acid ester insoluble in water as a precipitate; and (3) a method in which a large amount of water is added to the reaction solution.
しかしながら、前記（１）の方法では、溶媒の沸点が高
いため、溶媒除去時に高温を保つ必要があり、着色物質
の副生や、脂肪酸エステルの分解が避けられない。However, in method (1), since the boiling point of the solvent is high, it is necessary to maintain a high temperature during solvent removal, and the by-product of colored substances and decomposition of fatty acid esters are unavoidable.
糖と脂肪酸ハライドより、糖脂肪酸エステルを合成する
場合、ピリジン、ピロリドン、Ｎ−メチル−２−ピロリ
ドン、アシルピロリジン、アシルモルホリン、アシルピ
ペリジン、ジメチルホルムアミド等の含窒素化合物を反
応溶媒とすることは知られている。［例えば、Ｆ、Ｓｃ
ｈｏｌｎｉｃｋｅｔｗａｓ、Ｊ、Ａｍ、Ｏｉｌ Ｃｈ
ｅｍ、Ｓｏｃ、、５１．８ （１９７４）参照］これら
の溶媒は比較的沸点の高いものが多い０例えばピリジン
（１１６℃、７６０ｍｍＨｇ以下同じ）、ピロリドン（
２５１℃）、Ｎ−メチル−２−ピロリドン（２１３℃）
、蟻酸モルホリド（２２３℃）、蟻酸ピペリジド（２２
２℃）、ジメチルホルムアミド（１５３℃）であり、従
って、減圧下に溶媒を除去する場合でも、加熱の必要が
ある。It is known that when synthesizing sugar fatty acid esters from sugars and fatty acid halides, nitrogen-containing compounds such as pyridine, pyrrolidone, N-methyl-2-pyrrolidone, acylpyrrolidine, acylmorpholine, acylpiperidine, and dimethylformamide are used as reaction solvents. It is being [For example, F, Sc
holnicketwas, J., Am., Oil Ch.
Em, Soc, 51.8 (1974)] These solvents often have relatively high boiling points. For example, pyridine (116°C, 760 mmHg or less), pyrrolidone (
251°C), N-methyl-2-pyrrolidone (213°C)
, formic acid morpholide (223°C), formic acid piperidide (223°C)
2°C) and dimethylformamide (153°C), therefore heating is required even when removing the solvent under reduced pressure.
前記（２）の方法では、反応溶媒の混合した水層にも、
糖脂肪酸エステルが分配するため収率の低下が著しく実
用的でない、前記（３）の方法では、エステル化度の高
い水に不溶な糖脂肪酸エステルを精製する場合に関して
報告されているに過ぎず、エステル化度の低い糖脂肪酸
エステルについては報告されていない。In the method (2) above, the aqueous layer containing the reaction solvent also contains
The method (3) above, in which the yield decreases significantly and is impractical due to distribution of the sugar fatty acid ester, has only been reported for the purification of water-insoluble sugar fatty acid esters with a high degree of esterification. Sugar fatty acid esters with a low degree of esterification have not been reported.
これはシ、糖に対して７倍モルの脂肪酸クロリドを反応
させ、水に不溶なシ望糖脂肪酸エステルのポリエステル
を合成するものであり、さらに反応溶液を２２倍容の水
の中に、そそぐものである。This involves reacting 7 times the molar amount of fatty acid chloride with sugar to synthesize a water-insoluble polyester of saccharide fatty acid ester, and then pouring the reaction solution into 22 times the volume of water. It is something.
（ＵＳＰ第２，８５３，４８５号参照）本発明は、糖に
対して等モル以下の脂肪酸ハライドを用いてエステル化
度の低い、水溶性の糖脂肪酸エステルを合成して、精製
する方法に関するものである。この精製時に、反応溶液
にも、水にも容易に溶解する糖脂肪酸エステルが反応溶
媒に、特定範囲の量の水′を加えると、沈澱物として得
られる現象を見い出したものである。(See USP No. 2,853,485) The present invention relates to a method for synthesizing and purifying water-soluble sugar fatty acid esters with a low degree of esterification using equimolar or less fatty acid halide to sugar. It is. During this purification, we discovered a phenomenon in which sugar fatty acid esters, which are easily soluble in both the reaction solution and water, are obtained as precipitates when a specific range of water is added to the reaction solvent.
即ち、本発明は、
含窒素化合物を反応溶媒として、糖に対して、等モル以
下の脂肪酸ハライドを用いて、糖脂肪酸エステルを合成
し、反応が充分に進行した反応溶液に、反応溶媒の０．
２〜３，０倍（容量）の水を添加して、その後、冷却し
て糖脂肪酸エステルを分離することを特徴とする糖脂肪
酸エステルの精製法を提供するものである。That is, in the present invention, a sugar fatty acid ester is synthesized using a nitrogen-containing compound as a reaction solvent and a fatty acid halide in an amount equal to or less than the mole of the sugar, and the reaction solution in which the reaction has sufficiently progressed is added with 0 of the reaction solvent. ．．
The present invention provides a method for purifying sugar fatty acid esters, which is characterized by adding 2 to 3.0 times (volume) water and then cooling to separate the sugar fatty acid esters.
本発明における糖脂肪酸エステルとは、アラビノース、
キシロース、リホース、グルコース、マンノース、ガラ
クトース、フラクトース、マルトース、トレハロース、
ラクトース、シュクロース、パラチノース、マンノビオ
ース、ラフィノース等の単糖、三糖、三糖類の炭素数８
〜２２の脂肪酸エステルである。The sugar fatty acid ester in the present invention includes arabinose,
xylose, rehose, glucose, mannose, galactose, fructose, maltose, trehalose,
Monosaccharides, trisaccharides, and trisaccharides such as lactose, sucrose, palatinose, mannobiose, and raffinose have 8 carbon atoms.
~22 fatty acid esters.
また、本発明における含窒素化合物とは、ピリジン、ピ
ロリドン及びその誘導体１例えば、Ｎ−メチル−２−ピ
ロリドン等、アシルピロリジン、アシルモルホリン、ア
シルピペリジン、ジメチルホルムアミド等である。Further, the nitrogen-containing compounds in the present invention include pyridine, pyrrolidone and derivatives thereof, such as N-methyl-2-pyrrolidone, acylpyrrolidine, acylmorpholine, acylpiperidine, dimethylformamide and the like.
本発明は、先ず、従来の方法に従い、含窒素化合物を反
応溶媒として、糖と脂肪酸ハライドより、糖脂肪酸エス
テルを合成する。In the present invention, first, a sugar fatty acid ester is synthesized from a sugar and a fatty acid halide using a nitrogen-containing compound as a reaction solvent according to a conventional method.
この場合、使用する溶媒は単一、もしくは二種以上の混
合溶媒であってもよい。In this case, the solvent used may be a single solvent or a mixed solvent of two or more.
本発明において用いる脂肪酸ハライドの使用量は、糖に
対して等モル以下である。The amount of fatty acid halide used in the present invention is equal to or less than the amount of sugar.
次に、 反応が充分に進行した反応溶液に、水を添加す
る。添加する水め量は反応溶媒の０．２〜３．０倍（容
量）であり、好ましくは０．５〜１倍（容量）である、
添加する水の量が少ない場合、糖脂肪酸エステルの回収
率が低く、また多量に添加していくと、糖脂肪酸エステ
ルの沈殿は再度溶解してしまうので好ましくない。Next, water is added to the reaction solution in which the reaction has sufficiently progressed. The amount of water added is 0.2 to 3.0 times (volume) of the reaction solvent, preferably 0.5 to 1 times (volume).
If the amount of water added is small, the recovery rate of the sugar fatty acid ester will be low, and if a large amount of water is added, the precipitate of the sugar fatty acid ester will dissolve again, which is not preferable.
水を添加した後、溶液を冷却、例えば氷冷する。After adding water, the solution is cooled, for example on ice.
温度が高い場合、糖脂肪酸エステルの回収率は低い、水
を添加した際、その系を、酸性〜中性に調整する。When the temperature is high, the recovery rate of sugar fatty acid ester is low. When water is added, the system is adjusted to be acidic to neutral.
糖脂肪酸エステルの沈殿物は通常の方法で、例えば、濾
過、遠心分離、デカンテーション等により分離する。The precipitate of sugar fatty acid ester is separated by conventional methods such as filtration, centrifugation, decantation, etc.
本発明精製法による利点を挙げると、次の通りである。The advantages of the purification method of the present invention are as follows.
（１）本発明は、特に加熱を必要とせず、且つ高収率で
エステル化度の低い糖脂肪酸エステルを得ることができ
る。(1) The present invention does not particularly require heating, and can obtain sugar fatty acid esters with a high yield and a low degree of esterification.
（２）精製時、高温に保つ必要がないため、着色、分解
が発生しない。(2) Since there is no need to maintain high temperatures during purification, coloring and decomposition do not occur.
（３）精製操作が極めて簡単である。(3) Purification operation is extremely simple.
以下、本発明を実施例により具体的に説明する。Hereinafter, the present invention will be specifically explained with reference to Examples.
実施例１
５００ｍｌの４つロフラスコに撹拌器、滴下口斗、温度
計、冷却器を接続した。Example 1 A 500 ml four-loaf flask was connected to a stirrer, a dropping spout, a thermometer, and a condenser.
乳糖−水和物２８．８ｇを２００ｍ１のＮ−メチル−２
−ピロリドンに９０℃まで加熱し溶解させた。８０℃ま
で放冷したのち、３ｍｍＨｇで３０分間脱水した。28.8 g of lactose-hydrate and 200 ml of N-methyl-2
- Dissolved in pyrrolidone by heating to 90°C. After cooling to 80° C., dehydration was performed at 3 mmHg for 30 minutes.
溶液を４５℃まで放冷したのち無水ピリジン４０ｍ１を
加え、さらに、この溶液にステアリン酸クロリド８．１
ｇを２０ｍ１のＮ−メチル−２−ピロリドンに溶解させ
たものを滴下した。After cooling the solution to 45°C, 40ml of anhydrous pyridine was added, and 8.1ml of stearic acid chloride was added to the solution.
g was dissolved in 20 ml of N-methyl-2-pyrrolidone and added dropwise.
滴下終了後、４５℃で２０分間撹拌し、反応を行なった
０反応溶液に水２１０ ｍ ｌを加えた。また水酸化ナ
トリウムでＰＨ６，８に調節した。溶液を氷冷し、吸引
濾過で２０．９ｇの沈澱物を得た、反応溶液および、沈
澱物をＴＣＬにより定量した結果、乳糖ステアリン酸エ
ステルの精製時の回収率は９８．１％であった。After the dropwise addition was completed, the mixture was stirred at 45° C. for 20 minutes, and 210 ml of water was added to the reaction solution. Further, the pH was adjusted to 6.8 with sodium hydroxide. The solution was cooled on ice, and 20.9 g of precipitate was obtained by suction filtration. The reaction solution and precipitate were quantified by TCL, and the recovery rate of lactose stearate during purification was 98.1%. .
また、エステル組成はモノエステル：ジエステル＝８５
．３： １４．７であった。Also, the ester composition is monoester: diester = 85
．． 3: It was 14.7.
実施例２
ショ糖２７．４ｇとパルミチン酸クロリド７．３ｇを用
いて、実施例１と同様に操作し、ショ糖パルミチン酸エ
ステルを合成した０反応溶液に水２１０ ｍ ｌを加え
、水酸化ナトリウムでＰＨ８、８に調節した。Example 2 27.4 g of sucrose and 7.3 g of palmitic acid chloride were used to synthesize sucrose palmitic acid ester in the same manner as in Example 1. 210 ml of water was added to the reaction solution, and sodium hydroxide was added. The pH was adjusted to 8.8.
溶液を氷冷し、吸引濾過で１９．８ｇの沈澱物を得た０
反応溶液および、沈澱物をＴＣＬにより定量した結果、
ショ糖パルミチン酸エステルの精製時の回収率は９７．
７％であった。The solution was cooled on ice, and 19.8 g of precipitate was obtained by suction filtration.
As a result of quantifying the reaction solution and precipitate by TCL,
The recovery rate during purification of sucrose palmitate was 97.
It was 7%.
また、エステル組成はモノエステル：ジエステル＝９０
．３：９．７であった。Also, the ester composition is monoester: diester = 90
．． The ratio was 3:9.7.
比較例１ 実施例１と同様に反応を行なった。Comparative example 1 The reaction was carried out in the same manner as in Example 1.
反応溶液に水３０００ｍｌを加え、水酸化ナトリウムで
ＰＨ６，８に調節した。3000 ml of water was added to the reaction solution, and the pH was adjusted to 6.8 with sodium hydroxide.
その結果、溶液は白濁するのみで、沈澱物は得られなか
った。As a result, the solution only became cloudy and no precipitate was obtained.
比較例２ 実施例１と同様に反応を行なった。Comparative example 2 The reaction was carried out in the same manner as in Example 1.
反応溶液を８０℃加熱、３ｍｍＨｇに減圧し、溶媒を除
去し、淡褐色の残渣４２．６ｇを得た。The reaction solution was heated to 80° C., the pressure was reduced to 3 mmHg, and the solvent was removed to obtain 42.6 g of a pale brown residue.
残液をメチルエチルケトン１００ｍ１．水１００ｍ１に
溶解させ、５５に保持しつつ、水層を除去した。Pour the remaining liquid into 100 ml of methyl ethyl ketone. It was dissolved in 100 ml of water, and the aqueous layer was removed while maintaining the temperature at 55 ml.
メチルエチルケトン層を取りエバポレーターでメチルエ
チルケトンを除去し、固形物４．９ｇを得た。The methyl ethyl ketone layer was taken and the methyl ethyl ketone was removed using an evaporator to obtain 4.9 g of solid matter.
乳糖ステアリン酸エステルの回収率は３２．８％であっ
た。The recovery rate of lactose stearate was 32.8%.
またエステル組成は、モノエステル：ジエステル＝８０
．５： １９．５であった。Also, the ester composition is monoester: diester = 80
．． 5: It was 19.5.
Claims (1)
下の脂肪酸ハライドを用いて、糖脂肪酸エステルを合成
し、反応が充分に進行した反応溶液に、反応溶媒の０．
２〜３．０倍（容量）の水を添加して、その後、冷却し
て糖脂肪酸エステルを分離することを特徴とする糖脂肪
酸エステルの精製法。A sugar fatty acid ester is synthesized using a nitrogen-containing compound as a reaction solvent and an equimolar amount or less of fatty acid halide relative to sugar, and 0.0% of the reaction solvent is added to the reaction solution in which the reaction has sufficiently progressed.
A method for purifying sugar fatty acid esters, which comprises adding 2 to 3.0 times (volume) water and then cooling to separate the sugar fatty acid esters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60094446A JPS61251695A (en) | 1985-04-30 | 1985-04-30 | Purification of saccharide fatty acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60094446A JPS61251695A (en) | 1985-04-30 | 1985-04-30 | Purification of saccharide fatty acid ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61251695A true JPS61251695A (en) | 1986-11-08 |
Family
ID=14110484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60094446A Pending JPS61251695A (en) | 1985-04-30 | 1985-04-30 | Purification of saccharide fatty acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61251695A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0285178A2 (en) * | 1987-04-03 | 1988-10-05 | Meito Sangyo Co., Ltd. | Mannobiose derivatives |
| EP0507323A2 (en) * | 1991-04-05 | 1992-10-07 | Lion Corporation | Process for preparing fatty acid esters of saccharides |
-
1985
- 1985-04-30 JP JP60094446A patent/JPS61251695A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0285178A2 (en) * | 1987-04-03 | 1988-10-05 | Meito Sangyo Co., Ltd. | Mannobiose derivatives |
| EP0507323A2 (en) * | 1991-04-05 | 1992-10-07 | Lion Corporation | Process for preparing fatty acid esters of saccharides |
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