JP2000050895A - Chitinase inhibitor and production of chitinase inhibiting substance - Google Patents
Chitinase inhibitor and production of chitinase inhibiting substanceInfo
- Publication number
- JP2000050895A JP2000050895A JP10224497A JP22449798A JP2000050895A JP 2000050895 A JP2000050895 A JP 2000050895A JP 10224497 A JP10224497 A JP 10224497A JP 22449798 A JP22449798 A JP 22449798A JP 2000050895 A JP2000050895 A JP 2000050895A
- Authority
- JP
- Japan
- Prior art keywords
- chitinase
- compound
- belonging
- inhibitor
- methanol
- 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.)
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Links
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Saccharide Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、キチナーゼ阻害活
性を有する化合物の新規な製造方法及びその化合物を利
用した新規なキチナーセ阻害剤に関するものである。こ
のキチナーゼ阻害剤は抗菌剤、殺虫剤、農薬、船底塗料
などに利用することができる。TECHNICAL FIELD The present invention relates to a novel method for producing a compound having chitinase inhibitory activity and a novel chitinase inhibitor using the compound. This chitinase inhibitor can be used for antibacterial agents, insecticides, pesticides, ship bottom paints and the like.
【０００２】[0002]
【従来の技術】キチンはN-アセチル-D-グルコスアミン
（N-acetyl-D-glucosamine）がβ-1,4結合で重合した構
造多糖であり、自然界では、昆虫の皮膚、エビやカニの
殻、真菌類の細胞壁などに存在する。昆虫や甲殻類にお
いては、脱皮、成長の過程で、キチンの合成と分解およ
び再利用が行われることが知られている。また、カビ、
酵母などの真菌類は、***および増殖の過程でキチンの
合成と分解が制御されている。2. Description of the Related Art Chitin is a structural polysaccharide obtained by polymerizing N-acetyl-D-glucosamine through β-1,4 bonds. In nature, chitin is the skin of insects, shrimp and crab shells. Are present in fungal cell walls and the like. In insects and crustaceans, it is known that chitin is synthesized, decomposed and reused in the process of molting and growth. Also mold,
In fungi such as yeast, synthesis and degradation of chitin are controlled during the process of division and growth.
【０００３】キチナーゼは、キチンをN-アセチルキトビ
オースにまで分解する酵素であり、キチンの代謝系に関
わる主要な酵素である。キチンは哺乳類には存在しない
ことより、選択性の高い昆虫成育制御物質や抗菌剤を開
発する上での理想的来なターゲットの１つであると考え
られている（日本農芸化学会誌、作田庄平 1995年、6
9、147−153）。従って、キチナーゼに対する阻害剤
は、新しいタイプの抗真菌剤あるいは昆虫成長調節剤と
なり得、更には殺虫剤、殺ダニ剤になることが期待され
る。また、船底に付着する汚損生物であるフジツボなど
の甲殻類の脱皮を妨げることにより、甲殻類の付着阻害
物質として船底塗料などに使用されることも期待され
る。[0003] Chitinase is an enzyme that degrades chitin to N-acetylchitobiose and is a major enzyme involved in the metabolic system of chitin. Because chitin does not exist in mammals, it is considered to be one of the ideal targets for developing highly selective insect growth regulators and antibacterial agents (Japanese Journal of Agricultural Chemistry, Shohei Sakuta) 1995, 6
9, 147-153). Therefore, an inhibitor for chitinase can be a new type of antifungal agent or insect growth regulator, and is expected to be an insecticide or acaricide. It is also expected to be used in ship bottom paints and the like as a crustacean adhesion inhibitory substance by preventing the molting of crustaceans such as barnacles, which are fouling organisms that adhere to the bottom of ships.
【０００４】これまでに、キチナーゼ阻害物質として
は、アロサミジンおよびその誘導体（バイオサイエンス
とインダストリー、作田庄平 1993年、51、18−23）、
スティログアニジンおよびその誘導体（特開平8-198877
号公報）などが知られている。しかしながら、キチナー
ゼは生物種において異なるため、より多様なキチナーゼ
阻害物質の開発が望まれている。[0004] Hitherto, as chitinase inhibitors, allosamidine and its derivatives (Bioscience and Industry, Shohei Sakuta 1993, 51, 18-23),
Styloganidine and its derivatives (Japanese Patent Application Laid-Open No. 8-198877
No. 1). However, since chitinase differs in biological species, development of more diverse chitinase inhibitors has been desired.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、抗真菌剤、
殺虫剤、農薬、付着阻害剤などに有用な新規なキチナー
ゼ阻害剤を提供することを目的とする。The present invention relates to an antifungal agent,
An object is to provide a novel chitinase inhibitor useful as an insecticide, a pesticide, an adhesion inhibitor, and the like.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、キチナー
ゼに対する阻害活性を指標に天然界より検索した結果、
ハプト藻の一種が産生する糖脂質が非常に強いキチナー
ゼ阻害活性を有することを見出し、本発明を完成するに
至った。即ち、本発明は、下記の式（Ｉ）Means for Solving the Problems The present inventors have conducted a search from the natural world using chitinase inhibitory activity as an index, and found that
The present inventors have found that glycolipids produced by a kind of haptoalga have very strong chitinase inhibitory activity, and completed the present invention. That is, the present invention provides the following formula (I)
【０００７】[0007]
【化３】 Embedded image
【０００８】で表される化合物を有効成分として含有す
ることを特徴とするキチナーゼ阻害剤である。また、ハ
プト藻類に属する微細藻を培養することにより下記の式
（Ｉ）A chitinase inhibitor comprising a compound represented by the formula (1) as an active ingredient. Further, by culturing microalgae belonging to haptoalgae, the following formula (I)
【０００９】[0009]
【化４】 Embedded image
【００１０】で表される化合物を採取することを特徴と
する式（Ｉ）で表される化合物の製造方法である。A method for producing a compound represented by the formula (I), which comprises collecting the compound represented by the formula (I).
【００１１】[0011]
【発明の実施の形態】以下本発明を詳細に説明する。本
発明でキチナーゼ阻害剤として使用する化合物（以下、
この化合物を「化合物A」という）は、以下の理化学的
性質を示す。 1.物質の色：白色 2.分子量：512 3.分子式：C27H44O9 4.1H-NMR （重メタノール中で測定、500MHz） * （）内は多重度、結合定数（Hz） δppm 0.98 (3H, t, 7.6), 1.41 (2H, m), 1.63 (2H,
m), 2.09 (2H, m), 2.11(2H, m), 2,36 (2H, m), 2.82
(2H, m), 3.47 (1H, dd, 3.17, 9.66), 3.50 (1H, ddd,
0.98, 5.37, 6.59), 3.52 (1H, dd, 7.57, 9.66), 3.6
9 (1H, m), 3.72(2H, dd, 5.37, 6.59), 3.74 (1H, m),
3.82 (1H,dd, 0.98, 3.17), 3.97 (1H,dd, 14.1, 6.
1), 4.22 (1H, d, 7.57), 5.03 (1H, m), 5.36 (1H,
m). 5.13C-NMR （重メタノール中で測定、500MHz） * （）内は多重度 δppm 14.8 (q), 25.8 (t), 26.6 (t), 28.0 (t), 30.
3 (t), 35.2 (t), 61.9(t), 62.7 (t), 69.0 (t), 70.4
(d), 72.6 (d), 74.9 (d), 75.0 (d), 76.9 (d), 105.
5 (d), 128.3 (d), 129.0 (d), 129.1 (d), 129.3 (d),
129.5 (d), 129.6 (d), 130.8 (d), 132.9 (d), 175.2
(s). 6.溶解度：メタノール、エタノール、ブタノール、酢酸
エチル、クロロホルムに易溶、水に難溶。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. Compounds used as chitinase inhibitors in the present invention (hereinafter, referred to as
This compound is referred to as “compound A”) shows the following physicochemical properties. 1. materials Color: white 2. Molecular weight: 512 3. Molecular formula: C 27 H 44 O 9 4. 1 H-NMR ( measured in deuterated methanol, 500 MHz) * () within the multiplicity, coupling constant (Hz) δppm 0.98 (3H, t, 7.6), 1.41 (2H, m), 1.63 (2H,
m), 2.09 (2H, m), 2.11 (2H, m), 2,36 (2H, m), 2.82
(2H, m), 3.47 (1H, dd, 3.17, 9.66), 3.50 (1H, ddd,
0.98, 5.37, 6.59), 3.52 (1H, dd, 7.57, 9.66), 3.6
9 (1H, m), 3.72 (2H, dd, 5.37, 6.59), 3.74 (1H, m),
3.82 (1H, dd, 0.98, 3.17), 3.97 (1H, dd, 14.1, 6.
1), 4.22 (1H, d, 7.57), 5.03 (1H, m), 5.36 (1H,
m). 5. 13 C-NMR (measured in deuterated methanol, 500 MHz) * () indicates multiplicity δ ppm 14.8 (q), 25.8 (t), 26.6 (t), 28.0 (t), 30.
3 (t), 35.2 (t), 61.9 (t), 62.7 (t), 69.0 (t), 70.4
(d), 72.6 (d), 74.9 (d), 75.0 (d), 76.9 (d), 105.
5 (d), 128.3 (d), 129.0 (d), 129.1 (d), 129.3 (d),
129.5 (d), 129.6 (d), 130.8 (d), 132.9 (d), 175.2
(s). 6. Solubility: Easily soluble in methanol, ethanol, butanol, ethyl acetate, chloroform, and poorly soluble in water.
【００１２】次に、化合物Aの製造法について説明す
る。本発明で用いられる微細藻類は化合物Ａを産生する
ものであれば特に限定されるものではないが、微細藻の
中でも、ハプト藻に属する微細藻を好ましく例示でき
る。ハプト藻に属する微細藻の中では、イソクリシス・
ガルバナ（Isochrysisgalbana）に属する微細藻を使用
するのが特に好ましい。微細藻類からの化合物Aの単離
精製は、天然物から単離精製するために常用される方法
に従って行われる。例えば、微細藻類をアセトン、メタ
ノール、水、含水メタノール、含水エタノール、エタノ
ールなどで抽出し、イオン交換樹脂、活性炭、ゲル濾過
剤、シリカゲルカアラムクロマトグラフィーや高速液体
クロマトグラヒウィーなどを使用することにより化合物
Ａを得ることができる。Next, a method for producing compound A will be described. The microalgae used in the present invention is not particularly limited as long as it produces compound A. Among the microalgae, microalgae belonging to haptoalgae can be preferably exemplified. Among microalgae belonging to haptoalgae, isochrysis
Particular preference is given to using microalgae belonging to the galvana (Isochrysisgalbana). Isolation and purification of compound A from microalgae are performed according to a method commonly used for isolation and purification from natural products. For example, microalgae are extracted with acetone, methanol, water, hydrated methanol, hydrated ethanol, ethanol, and the like, and ion-exchange resin, activated carbon, gel filtration agent, silica gel calam chromatography, high-performance liquid chromatography, and the like are used. Compound A can be obtained.
【００１３】これまで、化合物Aは、微細藻類の抽出液
からジアシルグリセロ糖脂質である化合物Ｂ〔（２
Ｓ’）−２’−Ｏ−（６，９，１２，１５−オクタデカ
テトラエノイル）−３’−Ｏ−（５，８，１１，１４，
１７−イコサペンタエノイル）グリセリルβ−Ｄ−ガラ
クトピラノシド〕を採取し、しかる後にこれを加水分解
するという２段階の工程で製造されることが報告されて
いるのみである(Chem. Pharm. Bull. 1992, 40, 1404-1
410)。加えて、加水分解反応において位置選択性が乏し
く、グリセロールの２位で加水分解が起きたもの及び３
位で加水分解が起きたものとの混合物となっており、反
応成績体相互の分離の工程が必須となっていた。すなわ
ち、化学的に純粋な化合物Ａを製造するには多工程を要
していた。今回、発明者らが示す方法では容易に採取す
ることができる。Heretofore, compound A has been prepared from a microalgal extract from compound B, which is a diacylglyceroglycolipid [(2
S ')-2'-O- (6,9,12,15-octadecatetraenoyl) -3'-O- (5,8,11,14,
17-icosapentaenoyl) glyceryl β-D-galactopyranoside], which is then reported to be produced in a two-step process (Chem. Pharm. Bull. 1992, 40, 1404-1
410). In addition, poor regioselectivity in the hydrolysis reaction, hydrolysis occurred at the 2-position of glycerol and 3
It was a mixture with the one in which hydrolysis occurred at the position, and the step of separating the reaction products was essential. That is, production of chemically pure compound A required many steps. This time, the method shown by the inventors can be easily collected.
【００１４】化合物Ａは、キチナーゼの酵素活性を阻害
するので、キチナーゼ阻害剤として用いることができ
る。また、そのキチナーゼ阻害活性を利用して抗真菌
剤、抗菌剤、殺虫剤、農薬、船底塗料などとしての用途
も考えられる。以下、実施例により本発明を更に説明す
る。Since compound A inhibits the enzyme activity of chitinase, it can be used as a chitinase inhibitor. The chitinase inhibitory activity may be used as antifungal agents, antibacterial agents, insecticides, pesticides, ship bottom paints, and the like. Hereinafter, the present invention will be further described with reference to examples.
【００１５】[0015]
【実施例】〔実施例１〕硝酸ナトリウム１２０ｍｇ/
Ｌ、りん酸二カリウム５ｍｇ/Ｌ，ビタミンＢ１２１μ
ｇ/Ｌ，ビタミンＢ１１００μｇ/Ｌ，ビオチン１μｇ/
Ｌ，Ｆｅ−ＥＤＴＡ２５９ｍｇ/Ｌ、Ｍｎ−ＥＤＴＡ３
３２ｍｇ/Ｌ、トリス緩衝液１ｇ/Ｌ、土壌抽出液５０ｍ
ｌ/Ｌ、海水１Ｌの組成を有するＥＳＭ培地（ｐＨ８．
０）８Ｌを１０Ｌのプラスチクボトルに加え、イソクリ
シス・ガルバナに属する微細藻株を種菌として植菌し
て、２５℃で、２−３週間培養した。[Example 1] Sodium nitrate 120 mg /
L, dipotassium phosphate 5mg / L, vitamin B121μ
g / L, vitamin B1100μg / L, biotin 1μg /
L, Fe-EDTA 259 mg / L, Mn-EDTA3
32 mg / L, Tris buffer 1 g / L, soil extract 50 m
1 / L, 1L of seawater, ESM medium (pH 8.
0) 8 L was added to a 10 L plastic bottle, and a microalga strain belonging to Isocrisis galvana was inoculated as a seed fungus and cultured at 25 ° C for 2-3 weeks.
【００１６】〔実施例２〕８０Ｌの培養液を１００００
ｒｐｍで連続遠心分離し、２０ｇの凍結乾燥藻体を得
た。これに１Ｌのアセトンを加えて抽出し、これを３回
繰り返した。得られた抽出液を減圧濃縮してアセトンを
除去した後、酢酸エチルと水を各１Ｌ加えて分配した。
酢酸エチル層は濃縮後、さらにヘキサンと７０％メタノ
ールで分配を行った。活性のある７０％メタノール画分
をシリカゲルカラムに吸着させ、クロロホルムーメタノ
ール（メタノール：０−１００％）で溶出した。次に、
活性成分を逆相カラム（東ソー社製、ＴＳＫｇｅｌＯＤ
Ｓ−８０Ｔｓ，２×２５ｃｍ）に吸着させ、アセトニト
リルー水で溶出する高速液体クロマトグラフィーによ
り、化合物Ａを８．２ｍｇ得た。Example 2 An 80 L culture solution was used in 10,000
Continuous centrifugation was performed at rpm to obtain 20 g of freeze-dried algal cells. To this, 1 L of acetone was added for extraction, and this was repeated three times. After the obtained extract was concentrated under reduced pressure to remove acetone, ethyl acetate and water (1 L each) were added and partitioned.
After concentration, the ethyl acetate layer was further partitioned with hexane and 70% methanol. The active 70% methanol fraction was adsorbed on a silica gel column and eluted with chloroform-methanol (methanol: 0-100%). next,
The active ingredient was subjected to a reverse phase column (TSKgelOD, manufactured by Tosoh Corporation).
(S-80Ts, 2 × 25 cm) and 8.2 mg of Compound A was obtained by high performance liquid chromatography eluting with acetonitrile water.
【００１７】〔実施例３〕化合物Ａのキチナーゼ阻害活
性を以下のように測定した。基質溶液として０．４ｍＭ
ｐ−ニトロフェニルージーＮ−アセチルーβ―キトビオ
サイド（P-nitrophenyl-di-N-acetyl-β-chitobiosid
e）（生化学工業社製）の５０ｍＭナトリウムリン酸緩
衝液（ｐＨ７．０）を用い、酵素溶液としてバチルス
（Ｂａｃｉｌｌｕｓ）属の微生物由来のキチナーゼ（シ
グマ社製）の１ｍｇ/ｍｌ（水溶液）を用いた。Example 3 The chitinase inhibitory activity of Compound A was measured as follows. 0.4 mM as substrate solution
P-nitrophenyl-di-N-acetyl-β-chitobiosid
e) Using 50 mM sodium phosphate buffer (manufactured by Seikagaku Corporation) (pH 7.0), 1 mg / ml (aqueous solution) of a chitinase (manufactured by Sigma) derived from a microorganism belonging to the genus Bacillus was used as an enzyme solution. Using.
【００１８】30℃にて通常の紫外可視分光光度計のセル
中に基質溶液９００μｌと、１ｍｇ/ｍｌの化合物Ａの
えたのーる溶液５０μｌを入れた。1分後に酵素溶液５
０μｌを添加し、20秒から80秒までの４０５ｎｍの吸光
度の増加を測定した。ブランク試験は化合物Ａを含まな
いエタノール溶液を用いた。化合物Ａを加えた場合（化
合物Ａの濃度：２５μｇ/ｍｌ）、ブランクと比較して
３０％の吸光度の減少が見られた。At 30 ° C., 900 μl of the substrate solution and 50 μl of a 1 mg / ml solution of Compound A were placed in a cell of a conventional ultraviolet-visible spectrophotometer. 1 minute later, enzyme solution 5
0 μl was added and the increase in absorbance at 405 nm from 20 seconds to 80 seconds was measured. In the blank test, an ethanol solution containing no compound A was used. When Compound A was added (concentration of Compound A: 25 μg / ml), a 30% decrease in absorbance as compared to the blank was observed.
【００１９】[0019]
【発明の効果】本発明は、新規なキチナーゼ阻害剤、及
びその阻害剤の有効成分とする化合物の容易な製造法を
提供する。Industrial Applicability The present invention provides a novel chitinase inhibitor and a method for easily producing a compound as an active ingredient of the inhibitor.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ１２Ｒ 1:89） Ｆターム(参考） 4B064 AF41 BA06 BE07 BE08 BE09 BE10 BE14 BG01 BH04 BH05 CA08 DA02 DA12 DA16 4C057 AA05 AA09 BB02 DD01 JJ12 4C086 AA03 AA04 EA04 MA04 NA14 ZB35 ZC20 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification FI FI Theme coat ゛ (Reference) C12R 1:89) F-term (Reference) 4B064 AF41 BA06 BE07 BE08 BE09 BE10 BE14 BG01 BH04 BH05 CA08 DA02 DA12 DA16 4C057 AA05 AA09 BB02 DD01 JJ12 4C086 AA03 AA04 EA04 MA04 NA14 ZB35 ZC20
Claims (3)
とするキチナーゼ阻害剤。(1) The following formula (I): A chitinase inhibitor comprising, as an active ingredient, a compound represented by the formula:
とにより下記の式（Ｉ） 【化２】 で表される化合物を採取することを特徴とする式（Ｉ）
で表される化合物の製造方法。2. A microalga belonging to the haptoalgae is cultured to obtain the following formula (I): A compound represented by the formula (I):
A method for producing a compound represented by the formula:
する微細藻であることを特徴とする請求項２記載の化合
物の製造方法。3. The method for producing a compound according to claim 2, wherein the microalgae is a microalga belonging to Isocrisis galvana.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10224497A JP2000050895A (en) | 1998-08-07 | 1998-08-07 | Chitinase inhibitor and production of chitinase inhibiting substance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10224497A JP2000050895A (en) | 1998-08-07 | 1998-08-07 | Chitinase inhibitor and production of chitinase inhibiting substance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000050895A true JP2000050895A (en) | 2000-02-22 |
Family
ID=16814732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10224497A Pending JP2000050895A (en) | 1998-08-07 | 1998-08-07 | Chitinase inhibitor and production of chitinase inhibiting substance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000050895A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007112759A (en) * | 2005-10-21 | 2007-05-10 | Biseibutsu Riyo Shinkino Busshitsu Seisan Gijutsu Kenkyu Kumiai | Insect pest feeding inhibitor and method |
| JP2012517476A (en) * | 2009-02-11 | 2012-08-02 | ダウ アグロサイエンシィズ エルエルシー | Insecticide composition |
-
1998
- 1998-08-07 JP JP10224497A patent/JP2000050895A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007112759A (en) * | 2005-10-21 | 2007-05-10 | Biseibutsu Riyo Shinkino Busshitsu Seisan Gijutsu Kenkyu Kumiai | Insect pest feeding inhibitor and method |
| JP2012517476A (en) * | 2009-02-11 | 2012-08-02 | ダウ アグロサイエンシィズ エルエルシー | Insecticide composition |
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