JPH0559708B2 - - Google Patents
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- Publication number
- JPH0559708B2 JPH0559708B2 JP60198613A JP19861385A JPH0559708B2 JP H0559708 B2 JPH0559708 B2 JP H0559708B2 JP 60198613 A JP60198613 A JP 60198613A JP 19861385 A JP19861385 A JP 19861385A JP H0559708 B2 JPH0559708 B2 JP H0559708B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- water
- ester
- alcohol
- lipase
- 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.)
- Expired - Fee Related
Links
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 150000002148 esters Chemical class 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000004367 Lipase Substances 0.000 claims description 18
- 102000004882 Lipase Human genes 0.000 claims description 18
- 108090001060 Lipase Proteins 0.000 claims description 18
- 235000019421 lipase Nutrition 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 235000000346 sugar Nutrition 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 238000001308 synthesis method Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 150000005846 sugar alcohols Chemical class 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 2
- 239000000047 product Substances 0.000 description 10
- 150000001735 carboxylic acids Chemical class 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000032050 esterification Effects 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- -1 fatty acid ester Chemical class 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000008163 sugars Chemical class 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 229930006000 Sucrose Natural products 0.000 description 2
- 241000179532 [Candida] cylindracea Species 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 150000003626 triacylglycerols Chemical class 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- 241000228245 Aspergillus niger Species 0.000 description 1
- 241000235403 Rhizomucor miehei Species 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 239000000469 ethanolic extract Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000008173 hydrogenated soybean oil Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Description
【発明の詳細な説明】
(a) 産業上の利用分野
本発明は、エステル合成を低温でかつ効率よく
行う方法に関するものであり、特に糖類のカルボ
ン酸エステルに関して従来より著しく容易に品質
の良い製品を合成する方法に関するものである。[Detailed Description of the Invention] (a) Field of Industrial Application The present invention relates to a method for efficiently synthesizing esters at low temperatures, and in particular, it relates to a method for efficiently synthesizing esters of saccharides. It relates to a method of synthesizing.
(b) 従来の技術
従来、エステル合成の方法として溶媒中あるい
は無溶媒下において、カルボン酸とアルコールも
しくはそれらの誘導体を酸あるいはアルカリ触媒
の存在下で反応させることが知られており、あら
ゆる種類のエステルが工業的に合成されている。(b) Prior art Conventionally, it has been known that as a method for ester synthesis, a carboxylic acid and an alcohol or a derivative thereof are reacted in the presence of an acid or alkali catalyst in a solvent or in the absence of a solvent. Esters are industrially synthesized.
また、リパーゼによるエステル合成について
は、トリグリセリドをエステル交換した例（特開
昭52−104506、特開昭55−84397、特開昭57−
8787）、糖エステルを合成した例（清野ら、J.
Am.OilChem.Soc.，611761（1984）などがある。 In addition, regarding ester synthesis using lipase, examples of transesterification of triglycerides (JP-A-52-104506, JP-A-55-84397, JP-A-57-
8787), an example of sugar ester synthesis (Seino et al., J.
Am.OilChem.Soc., 61 1761 (1984), etc.
(c) 発明が解決しようとする問題点
通常行われている酸あるいはアルカリ触媒によ
るエステル合成は、一般に高温反応のため、エネ
ルギー的問題もさることながら着色や副生成物の
生成といつた副反応が生じる。(c) Problems to be Solved by the Invention The conventional ester synthesis using acid or alkali catalysts is generally a high-temperature reaction, which causes not only energy problems but also side reactions such as coloration and the formation of by-products. occurs.
着色は、あらゆるエステル化で問題となる。通
常は活性炭や白土などの脱色剤を用いたり、生成
物を減圧蒸留によつて得る方法が用いられてい
る。特に糖類のエステルは着色や分解・重合が生
じやすい。 Coloration is a problem in all esterifications. Usually, a method is used in which a decolorizing agent such as activated carbon or clay is used, or the product is obtained by distillation under reduced pressure. In particular, sugar esters are susceptible to coloring, decomposition, and polymerization.
次に副生成物についてみると糖誘導体であるソ
ルビトールのエステルは副反応により副生成物が
生じる典型的な例である。“SPAN”という商品
に代表されるソルビトールの脂肪酸エステルは、
ソルビタンエステルやソルビドエステルの混合物
となつている。これは、脂肪酸を脱水反応でエス
テル化する際に次に示すような分子内縮合が副反
応として生じるためである。 Next, regarding by-products, esters of sorbitol, which is a sugar derivative, are a typical example of by-products produced due to side reactions. The fatty acid ester of sorbitol represented by the product “SPAN” is
It is a mixture of sorbitan ester and sorbide ester. This is because the following intramolecular condensation occurs as a side reaction when fatty acids are esterified by dehydration.
これを防ぐためには、保護基を付けた後にエス
テル化するなどの特殊な反応を行う必要があつ
た。 In order to prevent this, it was necessary to perform a special reaction such as esterification after attaching a protecting group.
このような化学的手段によらず、リパーゼを用
いて反応を行えば上記の副反応を抑えることがで
きる。しかし水の存在下では加水分解方向に反応
が進みやすいため、トリグリセリドのエステル変
換においては、リバーゼの活性化に必要な最小限
の水の存在下での反応を行うことが必要で、この
ために反応初基の水分量コントロールにかなり注
意しなければならなかつた。例えば前記した特開
昭52−104506では基質の水分量を0.2〜１％とし
ており、特開昭55−84397号では水の存在なしに
有機溶媒中で反応を行い、また特開昭57−8787で
は可及的乾燥した基質を用いている。 Regardless of such chemical means, the above side reactions can be suppressed by carrying out the reaction using lipase. However, in the presence of water, the reaction tends to proceed in the direction of hydrolysis, so when converting triglycerides into esters, it is necessary to carry out the reaction in the presence of the minimum amount of water necessary for activation of reverse. Considerable care had to be taken to control the water content of the starting group. For example, in the above-mentioned JP-A-52-104506, the moisture content of the substrate is set to 0.2-1%, in JP-A-55-84397, the reaction is carried out in an organic solvent without the presence of water, and in JP-A-57-8787, the reaction is carried out in an organic solvent without the presence of water. We use as dry a substrate as possible.
さらに、油性基質でない場合には、基質どうし
の相溶性や乳化・分散性が悪くなり、相互の接触
効率が悪くなるという欠点があり、これを補うた
めに溶媒中で反応を行うことが提案されている。
しかし、アセトンやピリジンのように極性の強い
溶剤では、酵素が失活しやすく、使用可能な溶剤
は限られている。また、安全性の面からも溶剤を
使うことに対する抵抗もある。さらにまた、糖類
のように水溶性固体アルコールの場合は、無溶剤
かつ常温では固液反応となり、反応が進みにく
く、また酵素が失活しないような安全な溶剤が存
在しないため、前記した清野らの文献の如く水溶
液中で酵素反応を行う方法が考えられたが、商業
上有利ではない。 Furthermore, if the substrate is not oil-based, the compatibility, emulsification, and dispersibility of the substrates will be poor, and the mutual contact efficiency will be poor. To compensate for this, it has been proposed to carry out the reaction in a solvent. ing.
However, highly polar solvents such as acetone and pyridine tend to deactivate the enzyme, and the solvents that can be used are limited. There is also resistance to the use of solvents from the standpoint of safety. Furthermore, in the case of water-soluble solid alcohols such as sugars, a solid-liquid reaction occurs without a solvent and at room temperature, making it difficult for the reaction to proceed, and there is no safe solvent that will not deactivate the enzyme. A method of carrying out an enzymatic reaction in an aqueous solution was considered, as described in the literature, but it is not commercially advantageous.
本発明の目的は、以上の問題点が解決されたエ
ステル合成法を提供し、以つて種々のエステル、
特に糖類のエステルを効率良く製造することにあ
る。 The purpose of the present invention is to provide an ester synthesis method that solves the above problems, and thereby provides a method for synthesizing various esters,
In particular, the objective is to efficiently produce saccharide esters.
(d) 問題点を解決するための手属
本発明者らは、上記の目的を達成するため鋭意
検討を重ねた結果、リパーゼによるエステル化の
初期反応を水溶液中で行い、その後減圧下で水分
除去を行いながら反応させることにより高品質の
エステルが容易に得られることを見い出した。(d) Measures to solve the problem As a result of extensive studies to achieve the above object, the present inventors carried out the initial reaction of esterification using lipase in an aqueous solution, and then evaporated water under reduced pressure. It has been found that a high quality ester can be easily obtained by performing the reaction while removing the ester.
本発明は、かかる知見に基づいて完成されたも
ので、アルコールとカルボン酸、またはその一方
が該カルボン酸あるいは該アルコールのエステル
を基質として用いるアルコールとカルボン酸との
エステル合成に際し、初期反処をリパーゼ水溶液
中で行い、その後、減圧下で水分除去を行いなが
ら反応を進めることを特徴とするエステル合成法
である。 The present invention was completed based on this knowledge, and it is possible to perform an initial reaction when synthesizing an ester between an alcohol and a carboxylic acid, or one of them using the carboxylic acid or the ester of the alcohol as a substrate. This is an ester synthesis method characterized by carrying out the reaction in an aqueous lipase solution and then proceeding with the reaction while removing water under reduced pressure.
以下本発明につき詳しく説明する。 The present invention will be explained in detail below.
本発明に用いる基質は、通常エステル化される
アルコールとカルボン酸であればいずれでもよ
い。ここでいうアルコールとはアルコール性の
OH基を持つた物質であり、カルボン酸とはカル
ボキシル基を持つた物質である。また、基質の一
方をこのアルコールあるいはカルボン酸のエステ
ルとすることも可能である。すなわち本発明で
は、基質としてアルコールとカルボン酸、該カル
ボン酸のエステルと該アルコール、該アルコール
のエステルと該カルボン酸の三通りの組み合わせ
のなかから適宜に選択できる。しかし、本発明の
効果を最も有効に利用する見地から、好ましくは
基質の一方または両方が常温で固体かつ水溶性で
ある糖類やアミノ酸類を用いることが良い。特に
糖および糖アルコールを基質として用いることが
望ましい。 The substrate used in the present invention may be any alcohol and carboxylic acid that are normally esterified. Alcohol here refers to alcoholic
It is a substance that has an OH group, and a carboxylic acid is a substance that has a carboxyl group. It is also possible to use an ester of this alcohol or carboxylic acid as one of the substrates. That is, in the present invention, the substrate can be appropriately selected from three combinations: an alcohol and a carboxylic acid, an ester of the carboxylic acid and the alcohol, and an ester of the alcohol and the carboxylic acid. However, from the standpoint of most effectively utilizing the effects of the present invention, it is preferable to use saccharides or amino acids as one or both of the substrates that are solid at room temperature and water-soluble. In particular, it is desirable to use sugars and sugar alcohols as substrates.
本発明に用いるリパーゼとしては、基質に適し
たリパーゼを選択する。なお、ここで通常の緩衝
液中における基質特異性と本発明の系における基
質特異性には大きな差はない。特に糖および糖ア
ルコールのエステル合成にはCandida
cylindraceaのリパーゼが適している。また、固
定化されているリパーゼを使用してもよい。 As the lipase used in the present invention, a lipase suitable for the substrate is selected. Note that there is no major difference between the substrate specificity in a normal buffer and the substrate specificity in the system of the present invention. Candida, especially for ester synthesis of sugars and sugar alcohols.
cylindracea lipase is suitable. Alternatively, immobilized lipase may be used.
以上に示した基質とリパーゼをまず水溶液中で
均質化し反応する。この際、活性化剤、安定剤、
緩衝剤、乳化剤や分散剤を加えても良い。反応温
度を用いるリパーゼによつて異なるが、Candida
cylindraceaを用いる場合は30〜40℃が望ましい。 The substrate and lipase shown above are first homogenized in an aqueous solution and reacted. At this time, activators, stabilizers,
Buffers, emulsifiers and dispersants may also be added. The reaction temperature varies depending on the lipase used, but Candida
When using cylindracea, the temperature is preferably 30 to 40°C.
この水溶液中での反応を数時間行い、ある程度
エステル化物が生成した段階で、反応系を減圧に
して水分を留去しながら反応を行う。なお、ここ
で反応と同時に減圧して徐々に水分を留去しなが
ら反応を行うことも可能であるが、あまり早期に
水分が完全に除かれてしまうと反応系が不均一に
なるため、この方法は減圧度の調整に注意を要
す。減圧度は、反応温度と蒸気圧から予想でき
る。ここでも減圧度を良くしすぎると反応系を不
均一にするため、40℃で反応を行うときは数mmＨ
ｇ〜20mmＨｇが好ましい。 The reaction in this aqueous solution is carried out for several hours, and when a certain amount of esterified product has been produced, the reaction system is reduced in pressure and the reaction is carried out while water is distilled off. It is also possible to carry out the reaction while gradually distilling off the water by reducing the pressure at the same time as the reaction, but if the water is completely removed too early, the reaction system will become non-uniform. The method requires care in adjusting the degree of decompression. The degree of pressure reduction can be predicted from the reaction temperature and vapor pressure. Here too, if the degree of vacuum is too good, the reaction system will become non-uniform, so when carrying out the reaction at 40℃, several mmH
g to 20 mmHg is preferred.
反応後は通常の溶剤分別、蒸留、カラム精製な
どの方法により精製を行えば良い。 After the reaction, purification may be carried out by conventional methods such as solvent fractionation, distillation, and column purification.
(e) 実施例
実施例 １
グリセリン40ｇ、大豆硬化油200ｇ、水100mlに
Mucor miehei由来の固定化リパーゼ（Novo社）
１ｇを加え、60℃で激しく撹拌する。１時間後に
系内をアスピレーターで約20mmＨｇに減圧し、
徐々に水分を留去しながら、60℃でさらに５時間
反応を行う。生成物にヘキサン200mlを加え、濾
過する。濾液をアルカリ脱酸、水洗、乾燥する。
生成物約230ｇが得られモノグリセリド約60％、
ジグリセリド約30％、トリグリセリド約10％であ
つた。(e) Examples Example 1 40g of glycerin, 200g of hydrogenated soybean oil, 100ml of water
Immobilized lipase from Mucor miehei (Novo)
Add 1 g and stir vigorously at 60°C. After 1 hour, reduce the pressure in the system to approximately 20 mmHg using an aspirator.
The reaction is continued at 60° C. for an additional 5 hours while gradually distilling off water. Add 200 ml of hexane to the product and filter. The filtrate is deacidified with alkali, washed with water, and dried.
Approximately 230g of product was obtained, with a monoglyceride content of approximately 60%,
About 30% was diglyceride and about 10% triglyceride.
実施例 ２
グリセリン120ｇ、コハク酸80ｇ、水100mlに
Aspergillus niger由来のリパーゼ（天野製薬）
１ｇを加え、40℃で激しく撹拌する。３時間後に
系内を真空ポンプで約５mmＨｇに減圧し、徐々に
水分を留去しながら40℃でさらに10時間反応を行
う。生成物をエタノール300mlで抽出する。エタ
ノール溶液を濃縮、乾燥すると、粘性液体170ｇ
が得られた。このものは酸価230、ケン化価370で
あつた。Example 2 120g of glycerin, 80g of succinic acid, 100ml of water
Lipase from Aspergillus niger (Amano Pharmaceutical)
Add 1 g and stir vigorously at 40°C. After 3 hours, the pressure inside the system was reduced to about 5 mmHg using a vacuum pump, and the reaction was continued at 40° C. for another 10 hours while gradually distilling off water. Extract the product with 300 ml of ethanol. When the ethanol solution is concentrated and dried, it becomes 170g of viscous liquid.
was gotten. This product had an acid value of 230 and a saponification value of 370.
実施例 ３
ソルビトール80ｇ、オレイン酸130ｇ、水100ml
にCandida cylindraceaリパーゼ（名糖産業）20
ｇ、セライト20ｇを加え、40℃で激しく撹拌す
る。６時間後に系内を真空ポンプで約５mmＨｇに
減圧し、徐々に水分を留去しながら、40℃でさら
に10時間反応を行う。生成物をエタノール300ml
で抽出する。エタノール溶液を濃縮、乾燥する。
生成物として白色ペースト状物質約170ｇが得ら
れ、分子内縮合していないソルビトイルモノオレ
アートが約70％含まれていることが確認された。Example 3 Sorbitol 80g, oleic acid 130g, water 100ml
Candida cylindracea lipase (Meito Sangyo) 20
g and 20 g of Celite, and stir vigorously at 40°C. After 6 hours, the pressure inside the system was reduced to about 5 mmHg using a vacuum pump, and the reaction was continued at 40° C. for another 10 hours while gradually distilling off water. Add the product to 300ml of ethanol
Extract with Concentrate and dry the ethanol solution.
About 170 g of a white paste-like substance was obtained as a product, and it was confirmed that it contained about 70% of sorbitoyl monooleate that was not intramolecularly condensed.
実施例 ４
シヨ糖100ｇ、オレイン酸90ｇ、水100mlに
Candida cylindracea由来のリパーゼ（名糖産
業）20ｇ、セライト20ｇを加え、実施例１と同様
に反応、精製する。生成物として白色ペースト状
物質約150ｇが得られ、モノオレイン酸シヨ糖エ
ステルが約60％含まれていることが確認された。Example 4 Add 100g of sucrose, 90g of oleic acid, and 100ml of water.
Add 20 g of lipase derived from Candida cylindracea (Meito Sangyo) and 20 g of Celite, and react and purify in the same manner as in Example 1. Approximately 150 g of a white pasty substance was obtained as a product, which was confirmed to contain approximately 60% sucrose monooleate.
(f) 発明の効果
本発明によりもたらされる効果は次の通りであ
る。(f) Effects of the invention The effects brought about by the present invention are as follows.
リパーゼを用いた低温反応のため、ソルビト
ールエステルにみられる分子内縮合や糖エステ
ル合成時の顕著な着色といつた副反応が生じな
い。 Because it is a low-temperature reaction using lipase, side reactions such as intramolecular condensation seen in sorbitol esters and noticeable coloring during sugar ester synthesis do not occur.
リパーゼによるエステル合成を効率的に行う
ために、従来不可欠と言われていた初期水分量
を調整することなしに、かつ無溶剤で反応が行
える。 In order to efficiently perform ester synthesis using lipase, the reaction can be carried out without adjusting the initial water content, which was previously considered essential, and without using a solvent.
水溶性固体基質で特に問題となる水不在下反
応での基質、および酵素間の接触効率の悪さを
初期反応でエステル化には不都合とされる水を
利用することによつて解決できる。 The poor contact efficiency between the substrate and the enzyme in the reaction in the absence of water, which is a particular problem with water-soluble solid substrates, can be solved by using water, which is considered inconvenient for esterification, in the initial reaction.
以上により、リパーゼによるエステル化が効
率化され、従来困難とされていた低温で工業的
エステル化が可能となる。 As a result of the above, esterification using lipase becomes more efficient, and industrial esterification becomes possible at low temperatures, which was previously considered difficult.
Claims (1)
該カルボン酸あるいは該アルコールのエステルを
基質として用いるアルコールとカルボン酸とのエ
ステル合成に際し、初期反応をリパーゼ水溶液中
で行い、その後、減圧下で水分除去を行いながら
反応を進めることを特徴とするエステル合成法。 ２ 常温で固体かつ水溶性の基質を用いる特許請
求の範囲第１項記載のエステル合成法。 ３ アルコールが糖または糖アルコールである特
許請求の範囲第１項記載のエステル合成法。[Scope of Claims] 1. When synthesizing an alcohol and a carboxylic acid, or one of them using the carboxylic acid or the ester of the alcohol as a substrate, the initial reaction is carried out in an aqueous lipase solution, and then the reaction is carried out under reduced pressure. An ester synthesis method characterized by proceeding with the reaction while removing water below. 2. The ester synthesis method according to claim 1, which uses a substrate that is solid at room temperature and water-soluble. 3. The ester synthesis method according to claim 1, wherein the alcohol is a sugar or a sugar alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60198613A JPS6258992A (en) | 1985-09-10 | 1985-09-10 | Method of synthesizing ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60198613A JPS6258992A (en) | 1985-09-10 | 1985-09-10 | Method of synthesizing ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6258992A JPS6258992A (en) | 1987-03-14 |
| JPH0559708B2 true JPH0559708B2 (en) | 1993-08-31 |
Family
ID=16394100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60198613A Granted JPS6258992A (en) | 1985-09-10 | 1985-09-10 | Method of synthesizing ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6258992A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62195292A (en) * | 1986-02-21 | 1987-08-28 | Dai Ichi Kogyo Seiyaku Co Ltd | Production of fatty acid ester using lipase |
| JPS62262997A (en) * | 1986-05-02 | 1987-11-16 | ノボ ノルディスク アクティーゼルスカブ | Production of wax |
| JPS62289190A (en) * | 1986-06-05 | 1987-12-16 | Dai Ichi Kogyo Seiyaku Co Ltd | Production of fatty acid ester using lipase |
| US5288619A (en) * | 1989-12-18 | 1994-02-22 | Kraft General Foods, Inc. | Enzymatic method for preparing transesterified oils |
| ES2836774T3 (en) * | 2005-05-23 | 2021-06-28 | Epax Norway As | Concentration of fatty acid alkyl esters by enzymatic reactions with glycerol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS578787A (en) * | 1980-03-14 | 1982-01-18 | Fuji Oil Co Ltd | Esterification by enzyme |
| JPS6019495A (en) * | 1983-07-12 | 1985-01-31 | Asahi Denka Kogyo Kk | Ester exchange reaction of oil or fat using lipase |
| JPS6070094A (en) * | 1983-08-23 | 1985-04-20 | Dai Ichi Kogyo Seiyaku Co Ltd | Production of sugar-fatty acid ester |
-
1985
- 1985-09-10 JP JP60198613A patent/JPS6258992A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS578787A (en) * | 1980-03-14 | 1982-01-18 | Fuji Oil Co Ltd | Esterification by enzyme |
| JPS6019495A (en) * | 1983-07-12 | 1985-01-31 | Asahi Denka Kogyo Kk | Ester exchange reaction of oil or fat using lipase |
| JPS6070094A (en) * | 1983-08-23 | 1985-04-20 | Dai Ichi Kogyo Seiyaku Co Ltd | Production of sugar-fatty acid ester |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6258992A (en) | 1987-03-14 |
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