JPH0615480B2 - Acylating agent - Google Patents
Acylating agentInfo
- Publication number
- JPH0615480B2 JPH0615480B2 JP24197387A JP24197387A JPH0615480B2 JP H0615480 B2 JPH0615480 B2 JP H0615480B2 JP 24197387 A JP24197387 A JP 24197387A JP 24197387 A JP24197387 A JP 24197387A JP H0615480 B2 JPH0615480 B2 JP H0615480B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- acylating agent
- aqueous solution
- acylating
- long
- 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
Description
【発明の詳細な説明】 〔産業上の利用分野〕 （ただしＲは長鎖アルキル基である。）で表わされるア
ミノ酸のＮ−位のアシル化剤に関する。さらに詳しく
は、アミノ酸のアシル化反応に関して、特に水溶液中に
おいて長鎖アシル化を可能にする。優れたアシル化剤に
関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] (However, R is a long-chain alkyl group.) It relates to the N-position acylating agent of the amino acid. More specifically, it relates to the acylation reaction of amino acids, which enables long-chain acylation, especially in aqueous solution. It relates to an excellent acylating agent.
従来、アシル化試薬としては、酸ハロゲン化物が代表的
な叛応試薬として知られている。しかしながら酸ハロゲ
ン化物は反応性に関して優れているものの、安定性が悪
く、特に水溶液中での反応には、過判量を必要としてい
た。しかも刺激性があり、取り扱いには注意を要した。
このような問題点を解決するために、最近ではペンタク
ロロフェノール，ｐ−ニトロフェノール，Ｎ−ヒドロキ
シスクシンイミドに、目的とするアシル部分を導入した
活性エステルタイプのアシル化試薬や、アシルイミダゾ
ール類に代表される活性アミドタイプのアシル化試薬が
開発されている。Conventionally, as an acylating reagent, an acid halide has been known as a typical reaction reagent. However, although the acid halide is excellent in reactivity, it is poor in stability, and an excessive amount is required for the reaction particularly in an aqueous solution. Moreover, it was irritating and required careful handling.
In order to solve such problems, recently, pentachlorophenol, p-nitrophenol, and N-hydroxysuccinimide are represented by an active ester type acylation reagent in which an acyl moiety of interest is introduced, and acyl imidazoles. Active amide type acylating reagents have been developed.
しかしながらこれらのアシル化試薬においては、特に長
鎖アシル化の場合、化合物自体に水溶性あるいは親水性
がないために、水溶液中で反応を行う場合、水と相溶性
のある有機溶媒に溶解させたのち、水溶液中の基質と反
応を行わなければならず、生成物を取り出すためには、
反応系内から有機溶媒を留去しなければならない。さら
に反応によつて生じるヒドロキシ化合物の除去が困難で
あるために、再結晶あるいはクロマト的精製を実施しな
いと満足のゆく純度は得られないことがある。また、有
機溶媒に不安定な化合物、たとえばタンパク質やペプチ
ドを基質とした場合には、非常に効率の悪い反応とな
る。However, in these acylating reagents, particularly in the case of long-chain acylation, since the compound itself is not water-soluble or hydrophilic, when the reaction is carried out in an aqueous solution, it was dissolved in an organic solvent compatible with water. After that, it has to react with the substrate in the aqueous solution, and in order to take out the product,
The organic solvent must be distilled off from the reaction system. Furthermore, since it is difficult to remove the hydroxy compound generated by the reaction, satisfactory purity may not be obtained without recrystallization or chromatographic purification. Further, when a compound unstable to an organic solvent, such as a protein or peptide, is used as a substrate, the reaction becomes very inefficient.
本発明者は、前述の如き従来のアシル化試薬の欠陥を克
服するために鋭意検討を行つた結果、 一般式 （ただしＲは長鎖アルキル基である。）で表わされるス
ルホニウム化合物が、水溶液中においてアミノ酸の優れ
たアシル化機能を有することを発見した。The present inventor has conducted extensive studies to overcome the above-mentioned drawbacks of conventional acylating reagents, and as a result, the general formula It was discovered that the sulfonium compound represented by (wherein R is a long-chain alkyl group) has an excellent amino acid acylation function in an aqueous solution.
本化合物は４−ヒドロキシフェニルジメチルスルホニウ
ム メチルサルフェートとＲ−ＣＯ−Ｃｌ（ただしＲは
長鎖アルキル基）で表わされる長鎖脂肪酸クロリドとの
反応によつて得られるか、あるいはＲ−ＣＯＯＨ（ここ
でＲは上記定義に従う）と４−ヒドロキシフェニルジメ
チルスルホニウムメチルサルフェートにジシクロヘキシ
ルカルボジイミドを作用させることによって容易に合成
できる。This compound is obtained by the reaction of 4-hydroxyphenyldimethylsulfonium methylsulfate with a long chain fatty acid chloride represented by R-CO-Cl (where R is a long chain alkyl group), or R-COOH (wherein R is as defined above) and 4-hydroxyphenyldimethylsulfonium methylsulfate can be readily synthesized by reacting dicyclohexylcarbodiimide.
本発明の化合物においてアシル化試薬としての他に比類
のない特徴としては、化合物自体が親水性ないし水溶性
であり、このため、従来困難であったアミノ酸を水溶液
中温和な条件下で容易に長鎖アシル化することが可能と
なつた。しかも水溶液中での反応であることから、水溶
液のpHを調節し、アミノ酸あるいはペプチドのα−アミ
ノ基あるいは側鎖アミノ基のみを選択的にシアル化する
ことも可能である。A unique feature of the compound of the present invention other than as an acylating reagent is that the compound itself is hydrophilic or water-soluble, which makes it easy to elongate an amino acid, which was conventionally difficult, in an aqueous solution under mild conditions. Chain acylation was possible. Moreover, since the reaction is carried out in an aqueous solution, it is possible to adjust the pH of the aqueous solution and selectively sialyate only the α-amino group or side chain amino group of the amino acid or peptide.
以下実施例にて本発明を詳細にするが、本発明の有用性
は下記のみに限定されるものではない。Hereinafter, the present invention will be described in detail with reference to Examples, but the usefulness of the present invention is not limited to the following.
Ｎ−ε−パルミトイルリジンの合成 リジン塩酸塩１．８３ｇを水５０mlに溶解し、２Ｎ−Ｎ
ａＯＨ５mlを加え室温で攪はんした。反応器にpH電極を
取り付けpH１１．３にて４−（パルミトイルオキシ）フ
ェニルジメチルスルホニウムメチルサルフェート５ｇを
徐々に加えた。Synthesis of N- [epsilon] -palmitoyl lysine 1.83 g of lysine hydrochloride was dissolved in 50 ml of water to give 2N-N.
5 ml of aOH was added and the mixture was stirred at room temperature. A pH electrode was attached to the reactor, and 5 g of 4- (palmitoyloxy) phenyldimethylsulfonium methyl sulfate was gradually added at pH 11.3.
反応中、２時間pH１１．３を２Ｎ−ＮａＯＨで維持す
る。析出する白色結晶をろ過し、水、エタノールで洗浄
した。During the reaction, pH 11.3 is maintained with 2N NaOH for 2 hours. Precipitated white crystals were filtered and washed with water and ethanol.
結果は次の表に示す。またその他のアシル化剤（前記一
般式のＲを変えたもの）を使用して、上記実施例と同様
に反応させたＮ−ε−アシルリジンの合成結果もまとめ
て次の表に示す。The results are shown in the table below. In addition, the synthesis results of N-ε-acyl lysine reacted in the same manner as in the above Examples using other acylating agents (R in the above general formula was changed) are also summarized in the following table.
〔発明の効果〕 本発明に係るアシル化剤は、実施例記載のとおり、有用
な長鎖アシル化試薬として、たとえば生化学分野におい
て寄与することが判明した。 [Effects of the Invention] As described in Examples, the acylating agent according to the present invention was found to contribute as a useful long-chain acylating reagent, for example, in the field of biochemistry.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24197387A JPH0615480B2 (en) | 1987-09-25 | 1987-09-25 | Acylating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24197387A JPH0615480B2 (en) | 1987-09-25 | 1987-09-25 | Acylating agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6483029A JPS6483029A (en) | 1989-03-28 |
| JPH0615480B2 true JPH0615480B2 (en) | 1994-03-02 |
Family
ID=17082342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24197387A Expired - Fee Related JPH0615480B2 (en) | 1987-09-25 | 1987-09-25 | Acylating agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0615480B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7358408B2 (en) | 2003-05-16 | 2008-04-15 | Az Electronic Materials Usa Corp. | Photoactive compounds |
| JP2008220395A (en) * | 2007-03-08 | 2008-09-25 | Aso Seiyaku Kk | Package for first aid adhesive plaster |
| KR102409621B1 (en) * | 2022-02-23 | 2022-06-22 | 주식회사 오피렉스 | dressing band |
-
1987
- 1987-09-25 JP JP24197387A patent/JPH0615480B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6483029A (en) | 1989-03-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |