JP4235389B2 - New pyrrole derivatives - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、新規なピロール誘導体、およびその用途に関する。
【０００２】
【従来の技術】
従来、抗菌性物質に関しては多くの報告がある。ピロール誘導体についても医薬品、抗菌剤として多くの化合物が開発され利用されており、多くの抗菌性化合物が知られている。化学物質の生理作用はその構造に依存するところが大きく、なお、利用面に適したより有効な抗菌活性を有する新規な化合物が要望されている。
また、澱粉は水と共に加熱され糊化した後に食されるものであるが、糊化した澱粉は、その直後から経時的に老化と呼ばれる現象が始まる。澱粉の老化によって、食品の食感、食味、アミラーゼによる消化率の低下などが生じる。このため澱粉の老化防止あるいは糊化を促進することが試みられ、その手段として、例えば乳化剤や糖類を添加する方法やアルカリ等の化学的処理を行う方法などが知られている。しかし、それぞれに用途が限定されるなどの問題があり、これらに有効な化合物の開発が要望されている。
【０００３】
【発明が解決しようとする課題】
本発明は、上述のような事情に鑑み、抗菌作用、澱粉老化防止、澱粉糊化促進作用を有し、特に食品に適用した場合においても安全且つ食感を損なわない新規なピロール誘導体を提供することを課題とする。
【０００４】
【課題を解決するための手段】
本発明者等は、上記の課題を解決するべく、研究した結果、先にトウガラシからの抽出物に澱粉老化防止作用があることを見出し特許出願(特願2000−304784号)した。そして、さらに研究を進めた結果、トウガラシの一品種であるパプリカ(paprika:英名)果実からの抽出物に抗菌作用、澱粉老化防止作用、澱粉の糊化促進作用を有する物質を見出しこれを単離することに成功し、本発明を完成した。本発明者等によって見出された物質は分子式C9H10N4O3を有し、5-ヒドロキシメチル-2-フォルミルピロール骨格を有する新規化合物である。この化合物は後述する物理化学的性質から推定される。
【０００５】
本発明は、このような5-ヒドロキシメチル-2-フォルミルピロール骨格を有する新規化合物に関する。また、本発明はこの化合物を有効成分とする抗菌剤、澱粉老化防止剤、澱粉糊化促進剤に関するものである。
【０００６】
本発明化合物は、パプリカ、ピーマンなどのトウガラシに属する植物を抽出し、分離精製することによって得ることができる。抽出原料の植物は主にパプリカの果実を利用するのがよく、乾燥したものでも乾燥していないものでもよく、またパプリカ粉末として利用されている材料を用いることも、油性の溶剤で色素成分などを抽出した残渣を利用することもできる。抽出溶剤としては、本発明化合物を溶解できる溶剤であればよく、好適には水、メタノール、エタノールあるいはこれらの混合溶媒を用いる。また、予めヘキサンなどの低極性溶媒で脱脂、脱色処理をし、その後高極性の溶媒で抽出することにより、後の精製処理を容易にすることもできる。抽出温度や抽出時間あるいは溶媒の量などは、特に制限されることはなく、通常は原料の２〜10容量倍程度の溶媒を用いて、常温から溶媒の沸点以下の温度で1〜24時間程度抽出操作を行えばよい。また、回収量を向上させるために、使用する溶媒量や時間を適宜選択したり、溶媒を取り換え繰り返し抽出してもよい。抽出液は、必要に応じて、活性炭などによる脱色処理、濃縮処理などを行い、分離精製処理を行う。分離精製は、その性状を利用した通常の分離手段、例えば、溶媒分配抽出法、吸着クロマト、分配クロマトなど各種のクロマトグラフィーなどを単独でまたは適宜組み合わせて精製単離する。また、精製工程の途中においてピロール環の5位のヒドロキシメチル基にアセチル基を導入した誘導体として精製単離することもできる。例えば、アセチル基の導入は、粗精製品をピリジンに溶解し、氷水で冷却しながら無水酢酸を加えて常温で一晩反応させ、その後水を加えて、酢酸エチルで抽出し水で洗浄後、乾燥してクロロフォルム−メタノールを溶離剤とするシリカゲルカラムクロマトグラフィーによって分画単離する。置換基の導入は精製工程のどの段階で行ってもよいが、好ましくはある程度精製された段階で行う。
【０００７】
上述のようにして得られる本発明化合物は、後述する実施例に見られるように、酵母、グラム陽性菌、グラム陰性菌に対して抗菌力を有し、また糊化澱粉の老化を抑制する作用や澱粉の糊化を促進する作用があることが見出された。従って、本発明化合物を有効成分とする抗菌剤、澱粉の老化抑制剤あるいは澱粉の糊化促進剤として利用できる。本発明化合物をこれらの有効成分とする場合、好ましくは水やエタノールなどの溶液として、あるいは糖やデキストリンなどで希釈して用いる。その使用濃度は適用する対象によって適宜決められる。
【０００８】
本発明化合物は、抗菌剤として使用する場合は、種々の食品、例えばハム、ソーセージ類、ハンバーグ等に0.001〜0.1重量％添加することがよく、また澱粉の老化抑制剤あるいは澱粉の糊化促進剤として使用する場合は、澱粉質食品、例えばパン、インスタント麺、あるいは米飯に0.0001〜0.1重量％添加するとよい。これらの添加は製造工程のいかなる段階で行ってもよい。
【０００９】
以下実施例を挙げて本発明を詳しく説明する。
【実施例１】
(本発明化合物(I)の製造)
市販の粉末パプリカ1kgにn-ヘキサン5Lを添加して、常温で一晩攪拌しながら抽出した後固液分離して得られる固形分からヘキサンを除去した。この粉末に20%エタノールを5L添加して常温で一晩静置後固液分離して抽出液を得た。この抽出液を合成吸着剤HP2MG（三菱化成製）500mlを充填し20％エタノールで平衡化したカラムに流し、更に20％エタノール3Lを流して洗浄した。その後溶離液として60%エタノール2Lを流して回収し、40℃で減圧濃縮した。その1/100量を採取して減圧乾燥し、粗精製物１とした。残りに水100mlを添加して溶解し、酢酸エチルで3回抽出し、酢酸エチル層を採取した。酢酸エチル抽出液は無水硫酸ナトリウムを用いて脱水後、濃縮乾燥した（粗精製物２）。
このようにして得られた粗活性成分をシリカゲルを吸着剤としたカラムクロマトグラフィーで目的物質を含む画分を分画した。溶離液としてクロロフォルム−メタノールを用い25:1〜10:1までの直線グラジェントを行った。この画分を濃縮後、STR ODS-II（信和化工株式会社製）を用いた高速液体クロマトグラフィー（20〜50%メタノール）によって本発明化合物(I)を含む画分を分取し、濃縮乾固した（粗精製物３）。
更に、クロロフォルム−メタノール（93:7）を溶離液とするシリカゲルカラムクロマトグラフィーを行い、本発明化合物(I)20mgを得た。この化合物は、分子量、紫外部吸収スペクトル、赤外部吸収吸収スペクトル、NMR等の結果より、5-ヒドロキシメチル-2-フォルミルピロール誘導体であることが推定される。
【００１０】
実施例１で得られた本発明化合物(I)の物理化学的性質を以下に示す。
(ａ) 外観 淡色粘稠物
(ｂ) 分子量（EI-MS） 222；m/z222(M+)
(ｃ) 分子式 C9H10N4O3
(ｄ) 溶剤に対する溶解性：エタノール、メタノールに易溶、酢酸エチル、水に可溶、クロロフォルムに難溶。
(ｅ) 紫外部吸収スペクトル(MeOH) 257, 293nm
(ｆ) 赤外部吸収スペクトルIRγmax (KBr)cm-1: 3361, 2950, 2925, 1718, 1653, 1430, 1170
(ｇ) 1H-NMR(CD3CN)ppm：δ2.73(1H,dd,J=6.8,17.6Hz), 3.07(1H,dd, J=9.3,17.6Hz), 3.35(1H,s), 4.6(2H,s), 5.58(1H,tr,J=8.0Hz), 6.25(1H, d,J= 3.9Hz),7.06(1H,d,J=3.9Hz), 8.9(1H,s), 9.30(1H,s)
【００１１】
【実施例２】
（本発明化合物(II)の製造）
実施例１で得た本発明化合物(Ｉ)10mgをピリジン0.2mlに溶解し、氷水で冷却しながら無水酢酸0.05mlを添加し、常温で一晩放置した。その後5mlの水を加え、酢酸エチル3mlで5回抽出した。酢酸エチル層は1%の塩酸1mlで洗浄、更に水2mlで3回洗浄し、その後、無水硫酸ナトリウムを加えて乾燥後、減圧濃縮した。これをクロロフォルム−メタノール(100:0〜95:5)を溶離液とするシリカゲルカラムクロマトグラフィーによって分画し、本発明化合物（II）9mgを得た。この化合物は、分子量、紫外部吸収スペクトル、赤外部吸収スペクトル、NMR等の結果より、5-アセトキシメチル-2-フォルミルピロールの１位の置換体であることが確認された。また、置換基は5,6-ジヒドロ-4-オキソ-3(H)-1,2,3-トリアジンであり、その5位または6位と接合していることが考えられる。従って、本発明化合物(II)は、5-アセトキシメチル-2-フォルミルピロールの１位に5,6-ジヒドロ-4-オキソ-3(H)-1,2,3-トリアジンがそのトリアジン環の5位または6位で接合している、すなわち、1-(5,6-ジヒドロ-4-オキソ-3-(H)1,2,3-トリアジン-5-イル)- 5-アセトキシメチル-2-フォルミルピロール、または1-(5,6-ジヒドロ-4-オキソ-3-(H)1,2,3-トリアジン-6-イル)- 5-アセトキシメチル-2-フォルミルピロールである。
この物質0.5mgをとり常法によるエステル加水分解を行い精製して得られた物質は、シリカゲルTLCのRf値、HPLC(ODSカラム)による溶出時間、紫外部吸収スペクトル、1H-NMRスペクトルは原料である本発明化合物（I）と完全に一致したことから、本発明化合物(I)のアセチル誘導体であることが確認された。従って、
本発明化合物(I)は、5-ヒドロキシメチル-2-フォルミルピロールの１位に5,6-ジヒドロ-4-オキソ-3(H)-1,2,3-トリアジンがそのトリアジン環の5位または6位で接合している、すなわち、1-(5,6-ジヒドロ-4-オキソ-3-(H)1,2,3-トリアジン-5-イル)- 5-ヒドロキシメチル-2-フォルミルピロール、または1-(5,6-ジヒドロ-4-オキソ-3-(H)1,2,3-トリアジン-6-イル)- 5-ヒドロキシメチル-2-フォルミルピロールである。
【００１２】
実施例２で得られた本発明化合物(II)の物理化学的性質を以下に示す。
(1) 外観 淡色粘稠物
(2) 分子量（EI-MS） 264；m/z264(M+)
(3) 分子式 C11H12N4O4
(4) 溶剤に対する溶解性：エタノール、メタノールに易溶、クロロフォルム、水に可溶。
(5) 紫外部吸収スペクトル(50%MeOH) 260, 295nm
(6) 赤外部吸収スペクトルIRγmax (KBr)cm-1 : 3241, 1791, 1723, 1659, 1492, 1451, 1329, 1311, 1232, 1184, 1045, 915
(7) 1H-NMR(CD3CN)ppm：δ2.01(3H,s), 2.76(1H,dd,J=6.8,17.6Hz), 3.09(1H,dd,J=9.3,17.6Hz), 5.09(2H,s), 5.42(1H,tr,J=8.5Hz), 6.41(1H, d,J=3.9Hz), 7.1(1H,ｄ,J=3.9Hz), 9.08(1H,s), 9.39(1H,s)
(8) 13C-NMR(CD3CN)ppm: δ21.0, 38.4, 56.3, 58.3, 113.5, 126.6, 133.4, 139.7, 171.3, 175.6, 180.9
(9) 質量分析GCMS(EI): 264, 263, 222, 221, 205, 193, 165, 136, 124, 108, 106, 98, 79
【００１３】
【実施例３】
実施例１の粉末パプリカに代えてピーマンから本発明化合物(I)を以下のようにして製造した。市場から購入した新鮮なピーマン500gを粉砕し、40%エタノール500mlを加えて抽出した。この抽出液を20%エタノールで平衡化させた50mlのダイヤイオン2MGを充填したカラムに通液し、20%エタノール500mlで洗浄後、60%エタノール100mlを流して回収した。この液を濃縮後10mlの水に溶解し、酢酸エチル50mlで抽出して抽出液を得た。この液を濃縮し、クロロフォルム−メタノール（93：7）を溶離液としたシリカゲルクロマトグラフィー、更に、ODSカラムを用いた高速液体クロマトグラフィーで40%メタノールで溶出し、本発明化合物(I)約1mgを得た。
【００１４】
【実施例４】
実施例１の粉末パプリカに代えてシシトウから本発明化合物(I)を以下のようにして製造した。市場から購入した新鮮なシシトウ500gを粉砕し、40%エタノール500mlを加えて抽出した。この抽出液を20%エタノールで平衡化させた50mlのダイヤイオン2MGを充填したカラムに通液し、20%エタノール500mlで洗浄後、60%エタノール100mlを流して回収した。この液を濃縮後10mlの水に溶解し、酢酸エチル50mlで抽出して抽出液を得た。この液を濃縮し、クロロフォルム−メタノール（93：7）を溶離液としたシリカゲルクロマトグラフィー、更に、ODSカラムを用いた高速液体クロマトグラフィーで40%メタノールで溶出し、本発明化合物(I)約0.8mgを得た。
【００１５】
【実施例５】
（抗菌力試験）
本発明化合物(I)および(II)が抗菌力は、次の試験によって確認した。試験の対象菌には酵母Saccharomyces cerevisiae IFO 0203、グラム陽性菌としてBacills subtilis IFO 3007、グラム陰性菌としてEschelichia coli K-12 IFO 3301を用いた。抗菌試験は8mm径のペーパーディスクを用いるペーパーディスク法で行い、ペーパーディスクに本発明化合物(I)および(II)を別々に10μgづつ含浸させたときの阻止円径を求めた。なお、Bacills subtilis、Eschelichia coliについては、普通ブイヨン寒天培地で30℃2日間培養後、Saccharomyces cerevisiaeについてはポテトデキストロース寒天培地で25℃５日間培養後、それぞれ判定した。結果を表１に示す。
【００１６】
【表１】
【実施例６】
（澱粉老化抑制試験）
米160gを洗浄後、水240mlと本発明化合物(I)、本発明化合物(II)および比較例として粗精製物１，２，３（実施例１参照）をそれぞれ20μgを加えて炊飯した。同様に本発明化合物を添加しない対照区を調製した。得られた炊飯を10℃で20時間保存した。保存前後の糊化度をBAP法で測定し、その差を算出して老化度とした。結果を表２に示す。
【００１８】
【表２】
【００１９】
【実施例７】
糊化促進試験は、次のよう行った。本発明化合物(I)または(II)10μg添加した１％の馬鈴薯澱粉溶液50mlを100℃で10分間加熱した。糊化度は600nmにおける透過度を測定した。また、この液を2倍に希釈して１％のヨウ素液を0.5ml添加して610nmのODを測定することで行った。結果を表３に示す。
【００２０】
【表３】
【発明の効果】
本発明化合物(I)および(II)は、新規化合物であって、従来食されている食品から得られ、抗菌作用、澱粉の老化抑制作用および糊化促進作用を兼ね備えている。従って、澱粉含有食品に添加することによって、調理後の保存性を増し、保存後においても美味しく食することができる。また、澱粉含有食品以外の食品に添加してその保存性を高めることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel pyrrole derivative and use thereof.
[0002]
[Prior art]
There have been many reports on antibacterial substances. As for pyrrole derivatives, many compounds have been developed and used as pharmaceuticals and antibacterial agents, and many antibacterial compounds are known. The physiological action of a chemical substance largely depends on its structure, and there is a demand for a novel compound having more effective antibacterial activity suitable for use.
In addition, starch is eaten after being heated and gelatinized with water, and the gelatinized starch starts a phenomenon called aging over time immediately after that. The aging of starch causes a decrease in food texture, taste and digestibility by amylase. For this reason, attempts have been made to prevent aging of starch or to promote gelatinization, and as its means, for example, a method of adding an emulsifier or saccharide, a method of performing chemical treatment such as alkali, and the like are known. However, there are problems such as limited applications, and there is a demand for the development of compounds effective for these.
[0003]
[Problems to be solved by the invention]
In view of the circumstances as described above, the present invention provides a novel pyrrole derivative that has an antibacterial action, starch aging prevention, and starch gelatinization promoting action, and that is safe and does not impair the texture even when applied to foods. This is the issue.
[0004]
[Means for Solving the Problems]
As a result of researches to solve the above-mentioned problems, the present inventors have previously found that an extract from red pepper has a starch aging-preventing action and applied for a patent (Japanese Patent Application No. 2000-304784). As a result of further research, we found a substance that has antibacterial action, starch aging prevention action, and starch gelatinization promoting action in an extract from paprika (English name) fruit which is a kind of pepper. Successfully completed the present invention. The substance found by the present inventors is a novel compound having the molecular formula C 9 H 10 N 4 O 3 and having a 5-hydroxymethyl-2-formylpyrrole skeleton. This compound is estimated from the physicochemical properties described below.
[0005]
The present invention relates to a novel compound having such a 5-hydroxymethyl-2-formylpyrrole skeleton. The present invention also relates to an antibacterial agent, starch aging inhibitor, and starch gelatinization accelerator containing this compound as an active ingredient.
[0006]
The compound of the present invention can be obtained by extracting, separating and purifying plants belonging to red pepper, such as paprika and peppers. The plant used as the raw material for extraction should mainly use paprika fruits, which may be dried or not dried, and may be used as paprika powder. The residue extracted from can also be used. The extraction solvent may be any solvent that can dissolve the compound of the present invention, and water, methanol, ethanol, or a mixed solvent thereof is preferably used. Further, the subsequent purification treatment can be facilitated by degreasing and decoloring treatment with a low polarity solvent such as hexane in advance and then extracting with a high polarity solvent. The extraction temperature, extraction time or the amount of solvent is not particularly limited, and usually uses about 2 to 10 times the volume of the solvent as the raw material, and the temperature is from room temperature to the boiling point of the solvent for about 1 to 24 hours. An extraction operation may be performed. In order to improve the recovery amount, the amount and time of the solvent to be used may be appropriately selected, or the solvent may be replaced and extracted repeatedly. If necessary, the extract is subjected to decolorization treatment using activated carbon or the like, concentration treatment, etc., and separation and purification treatment is performed. Separation and purification is carried out by purifying and isolating conventional separation means utilizing the properties, for example, various types of chromatography such as solvent partition extraction, adsorption chromatography, partition chromatography and the like alone or in appropriate combination. Further, it can be purified and isolated as a derivative in which an acetyl group is introduced into the hydroxymethyl group at the 5-position of the pyrrole ring during the purification step. For example, the introduction of an acetyl group involves dissolving a crude product in pyridine, adding acetic anhydride while cooling with ice water and reacting at room temperature overnight, then adding water, extracting with ethyl acetate, washing with water, Dry and fractionally isolate by silica gel column chromatography eluting with chloroform-methanol. The introduction of the substituent may be carried out at any stage of the purification process, but is preferably carried out at a stage that has been purified to some extent.
[0007]
The compound of the present invention obtained as described above has antibacterial activity against yeast, gram-positive bacteria, and gram-negative bacteria, as shown in the examples described later, and also acts to suppress aging of gelatinized starch. And starch have been found to promote gelatinization. Accordingly, it can be used as an antibacterial agent comprising the compound of the present invention as an active ingredient, a starch aging inhibitor or a starch gelatinization accelerator. When the compound of the present invention is used as these active ingredients, it is preferably used as a solution such as water or ethanol, or diluted with sugar or dextrin. The concentration used is appropriately determined depending on the target to be applied.
[0008]
When used as an antibacterial agent, the compound of the present invention is preferably added in an amount of 0.001 to 0.1% by weight to various foods such as ham, sausages, hamburgers, etc., and also includes starch aging inhibitors or starch gelatinization accelerators. When used as a starchy food, for example, bread, instant noodles, or cooked rice may be added in an amount of 0.0001 to 0.1% by weight. These additions may be made at any stage of the manufacturing process.
[0009]
Hereinafter, the present invention will be described in detail with reference to examples.
[Example 1]
(Production of the present compound (I))
To 1 kg of commercially available powdered paprika, 5 L of n-hexane was added, extracted with stirring at room temperature overnight, and then hexane was removed from the solid content obtained by solid- liquid separation . To this powder, 5 L of 20% ethanol was added and left overnight at room temperature, followed by solid-liquid separation to obtain an extract. This extract was poured into a column filled with 500 ml of synthetic adsorbent HP2MG (Mitsubishi Kasei) and equilibrated with 20% ethanol, and further washed with 3 L of 20% ethanol. Thereafter, 2 L of 60% ethanol was poured as an eluent, and the mixture was collected and concentrated under reduced pressure at 40 ° C. 1/100 of the amount was collected and dried under reduced pressure to obtain crude purified product 1. The residue was dissolved by adding 100 ml of water, extracted three times with ethyl acetate, and the ethyl acetate layer was collected. The ethyl acetate extract was dehydrated with anhydrous sodium sulfate and concentrated to dryness (crude product 2).
The crude active ingredient thus obtained was subjected to column chromatography using silica gel as an adsorbent to fractionate a fraction containing the target substance. A linear gradient from 25: 1 to 10: 1 was performed using chloroform-methanol as the eluent. After concentrating this fraction, the fraction containing the compound (I) of the present invention was fractionated by high performance liquid chromatography (20-50% methanol) using STR ODS-II (manufactured by Shinwa Kako Co., Ltd.), concentrated and dried. Solidified (crude product 3).
Furthermore, silica gel column chromatography using chloroform-methanol (93: 7) as an eluent was performed to obtain 20 mg of the present compound (I). This compound is estimated to be a 5-hydroxymethyl-2-formylpyrrole derivative from the results of molecular weight, ultraviolet absorption spectrum, infrared absorption spectrum, NMR, and the like.
[0010]
The physicochemical properties of the compound (I) of the present invention obtained in Example 1 are shown below.
( a ) Appearance Light colored viscous material
( b ) Molecular weight (EI-MS) 222; m / z 222 (M +)
(C) molecular formula C 9 H 10 N 4 O 3
( d ) Solubility in solvents: Easily soluble in ethanol and methanol, soluble in ethyl acetate and water, hardly soluble in chloroform.
( e ) UV absorption spectrum (MeOH) 257, 293nm
( f ) Red external absorption spectrum IRγmax (KBr) cm -1 : 3361, 2950, 2925, 1718, 1653, 1430, 1170
( g ) 1 H-NMR (CD 3 CN) ppm: δ 2.73 (1H, dd, J = 6.8, 17.6 Hz), 3.07 (1H, dd, J = 9.3, 17.6 Hz), 3.35 (1H, s) , 4.6 (2H, s), 5.58 (1H, tr, J = 8.0Hz), 6.25 (1H, d, J = 3.9Hz), 7.06 (1H, d, J = 3.9Hz), 8.9 (1H, s) , 9.30 (1H, s)
[0011]
[Example 2]
(Production of Compound (II) of the Present Invention)
10 mg of the compound (I) of the present invention obtained in Example 1 was dissolved in 0.2 ml of pyridine, 0.05 ml of acetic anhydride was added while cooling with ice water, and the mixture was allowed to stand overnight at room temperature. Then 5 ml of water was added and extracted 5 times with 3 ml of ethyl acetate. The ethyl acetate layer was washed with 1 ml of 1% hydrochloric acid and further washed 3 times with 2 ml of water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. This was fractionated by silica gel column chromatography using chloroform-methanol (100: 0 to 95: 5) as an eluent to obtain 9 mg of the present compound (II). This compound was confirmed to be a substitution product at the 1-position of 5-acetoxymethyl-2-formylpyrrole from the results of molecular weight, ultraviolet absorption spectrum, infrared absorption spectrum, NMR and the like. Further, the substituent is 5,6-dihydro-4-oxo-3 (H) -1,2,3-triazine, which is considered to be bonded to the 5-position or 6-position thereof. Therefore, the compound (II) of the present invention has 5,6-dihydro-4-oxo-3 (H) -1,2,3-triazine as the triazine ring at the 1-position of 5-acetoxymethyl-2-formylpyrrole. Of 1- (5,6-dihydro-4-oxo-3- (H) 1,2,3-triazin-5-yl) -5-acetoxymethyl- 2-formylpyrrole, or 1- (5,6-dihydro-4-oxo-3- (H) 1,2,3-triazin-6-yl) -5-acetoxymethyl-2-formylpyrrole .
The substance obtained by subjecting 0.5 mg of this substance to purification by ester hydrolysis in the usual manner is the Rf value of silica gel TLC, elution time by HPLC (ODS column), UV absorption spectrum, 1 H-NMR spectrum Thus, it was confirmed that the compound was an acetyl derivative of the compound (I) of the present invention. Therefore,
The compound (I) of the present invention has 5,6-dihydro-4-oxo-3 (H) -1,2,3-triazine at the 1-position of 5-hydroxymethyl-2-formylpyrrole. 1- (5,6-dihydro-4-oxo-3- (H) 1,2,3-triazin-5-yl) -5-hydroxymethyl-2- Formylpyrrole, or 1- (5,6-dihydro-4-oxo-3- (H) 1,2,3-triazin-6-yl) -5-hydroxymethyl-2-formylpyrrole.
[0012]
The physicochemical properties of the compound (II) of the present invention obtained in Example 2 are shown below.
(1) Appearance Light colored viscous material
(2) Molecular weight (EI-MS) 264; m / z264 (M +)
(3) Molecular formula C 11 H 12 N 4 O 4
(4) Solubility in solvents: Easily soluble in ethanol and methanol, soluble in chloroform and water.
(5) UV absorption spectrum (50% MeOH) 260, 295nm
(6) Red external absorption spectrum IRγmax (KBr) cm -1 : 3241, 1791, 1723, 1659, 1492, 1451, 1329, 1311, 1232, 1184, 1045, 915
(7) 1 H-NMR (CD 3 CN) ppm: δ 2.01 (3H, s), 2.76 (1H, dd, J = 6.8, 17.6 Hz), 3.09 (1H, dd, J = 9.3, 17.6 Hz) , 5.09 (2H, s), 5.42 (1H, tr, J = 8.5Hz), 6.41 (1H, d, J = 3.9Hz), 7.1 (1H, d, J = 3.9Hz), 9.08 (1H, s) , 9.39 (1H, s)
(8) 13 C-NMR (CD 3 CN) ppm: δ21.0, 38.4, 56.3, 58.3, 113.5, 126.6, 133.4, 139.7, 171.3, 175.6, 180.9
(9) Mass spectrometry GCMS (EI): 264, 263, 222, 221, 205, 193, 165, 136, 124, 108, 106, 98, 79
[0013]
[Example 3]
The compound (I) of the present invention was produced from bell pepper instead of the powder paprika of Example 1 as follows. 500 g of fresh peppers purchased from the market were crushed and extracted by adding 500 ml of 40% ethanol. The extract was passed through a column packed with 50 ml of Diaion 2MG equilibrated with 20% ethanol, washed with 500 ml of 20% ethanol, and then collected by flowing 100 ml of 60% ethanol. This solution was concentrated, dissolved in 10 ml of water, and extracted with 50 ml of ethyl acetate to obtain an extract. This liquid was concentrated and eluted with 40% methanol by silica gel chromatography using chloroform-methanol (93: 7) as an eluent and further by high performance liquid chromatography using an ODS column. About 1 mg of the compound (I) of the present invention Got.
[0014]
[Example 4]
The compound (I) of the present invention was produced from shishitou instead of the powdered paprika of Example 1 as follows. 500 g of fresh shishito purchased from the market was crushed and extracted by adding 500 ml of 40% ethanol. The extract was passed through a column packed with 50 ml of Diaion 2MG equilibrated with 20% ethanol, washed with 500 ml of 20% ethanol, and then collected by flowing 100 ml of 60% ethanol. This solution was concentrated, dissolved in 10 ml of water, and extracted with 50 ml of ethyl acetate to obtain an extract. This liquid was concentrated, and eluted with 40% methanol by silica gel chromatography using chloroform-methanol (93: 7) as an eluent and further by high performance liquid chromatography using an ODS column, and the compound (I) of the present invention was about 0.8. mg was obtained.
[0015]
[Example 5]
(Antimicrobial test)
The antibacterial activity of the compounds (I) and (II) of the present invention was confirmed by the following test. Yeast Saccharomyces cerevisiae IFO 0203, Bacills subtilis IFO 3007 as gram-positive bacteria, and Eschelichia coli K-12 IFO 3301 as gram-negative bacteria were used as test target bacteria. The antibacterial test was carried out by the paper disk method using an 8 mm diameter paper disk, and the inhibition circle diameter when the compound (I) and (II) of the present invention were separately impregnated with 10 μg each was determined. Bacills subtilis and Eschelichia coli were determined after culturing in a normal bouillon agar medium at 30 ° C. for 2 days, and Saccharomyces cerevisiae was determined after culturing in a potato dextrose agar medium at 25 ° C. for 5 days. The results are shown in Table 1.
[0016]
[Table 1]
[Example 6]
(Starch aging inhibition test)
After washing 160 g of rice, 240 ml of water, 20 μg each of the present compound (I), the present compound (II) and roughly purified products 1, 2, 3 (see Example 1) as comparative examples were added to cook rice. Similarly, a control group to which the compound of the present invention was not added was prepared. The resulting cooked rice was stored at 10 ° C. for 20 hours. The degree of gelatinization before and after storage was measured by the BAP method, and the difference was calculated as the degree of aging. The results are shown in Table 2.
[0018]
[Table 2]
[0019]
[Example 7]
The gelatinization acceleration test was performed as follows. 50 ml of a 1% potato starch solution containing 10 μg of the compound (I) or (II) of the present invention was heated at 100 ° C. for 10 minutes. As the degree of gelatinization, the transmittance at 600 nm was measured. Further, this solution was diluted 2 times, 0.5 ml of 1% iodine solution was added, and OD at 610 nm was measured. The results are shown in Table 3.
[0020]
[Table 3]
【The invention's effect】
The compounds (I) and (II) of the present invention are novel compounds, which are obtained from conventionally eaten foods, and have an antibacterial action, a starch aging inhibiting action and a gelatinization promoting action. Therefore, by adding to starch-containing foods, preservability after cooking is increased, and delicious food can be eaten even after storage. Moreover, the preservability can be enhanced by adding to foods other than starch-containing foods.
Claims (6)
(ａ) 外観 淡色粘稠物
(ｂ) 分子量（EI-MS） 222；m/z222(M+)
(ｃ) 分子式 C9H10N4O3
(ｄ) 溶剤に対する溶解性：エタノール、メタノールに易溶、酢酸エチル、水に可溶、クロロフォルムに難溶
(ｅ) 紫外部吸収スペクトル(MeOH) 257, 293nm
(ｆ) 赤外部吸収スペクトルIRγmax (KBr)cm-1 : 3361, 2950, 2925, 1718, 1653, 1430, 1170
(ｇ) 1H-NMR(CD3CN)ppm：δ2.73(1H,dd,J=6.8,17.6Hz), 3.07(1H,dd, J=9.3,17.6Hz), 3.35(1H,s), 4.6(2H,s), 5.58(1H,tr,J=8.0Hz), 6.25(1H,d,J= 3.9Hz), 7.06(1H,d,J=3.9Hz), 8.9(1H,s), 9.30(1H,s)
かつそのアセチル体が下記（１）〜（９）の理化学的性質を示す5-ヒドロキシメチル-2-フォルミルピロール誘導体を有効成分とする抗菌剤。
(1) 外観 淡色粘稠物
(2) 分子量（EI-MS） 264；m/z264(M+)
(3) 分子式 C11H12N4O4
(4) 溶剤に対する溶解性：エタノール、メタノールに易溶、クロロフォルム、水に可溶
(5) 紫外部吸収スペクトル(50%MeOH) 260, 295nm
(6) 赤外部吸収スペクトルIRγmax (KBr)cm-1 : 3241, 1791, 1723, 1659, 1492, 1451, 1329, 1311, 1232, 1184, 1045, 915
(7)1H-NMR(CD3CN)ppm：δ2.01(3H,s),2.76(1H,dd,J=6.8,17.6Hz), 3.09(1H,dd,J=9.3,17.6Hz), 5.09(2H,s), 5.42(1H,tr,J=8.5Hz), 6.41(1H, d,J=3.9Hz), 7.1(1H,ｄ,J=3.9Hz), 9.08(1H,s), 9.39(1H,s)
(8) 13C-NMR(CD3CN)ppm: δ21.0, 38.4, 56.3, 58.3, 113.5, 126.6, 133.4, 139.7, 171.3, 175.6, 180.9
(9) 質量分析GCMS(EI): 264, 263, 222, 221, 205, 193, 165, 136, 124, 108,106, 98, 79 The extract obtained by extraction with a highly polar solvent from the fruit of the genus Capsicum is further purified by a process including partition extraction with ethyl acetate, chromatography using silica gel and chromatography using ODS. The following physicochemical properties (a) to (g) obtained are shown:
( a ) Appearance Light colored viscous material
( b ) Molecular weight (EI-MS) 222; m / z 222 (M +)
(C) molecular formula C 9 H 10 N 4 O 3
( d ) Solubility in solvents: Easily soluble in ethanol and methanol, soluble in ethyl acetate and water, hardly soluble in chloroform
( e ) UV absorption spectrum (MeOH) 257, 293nm
( f ) Red external absorption spectrum IRγmax (KBr) cm -1 : 3361, 2950, 2925, 1718, 1653, 1430, 1170
( g ) 1 H-NMR (CD 3 CN) ppm: δ 2.73 (1H, dd, J = 6.8, 17.6 Hz), 3.07 (1H, dd, J = 9.3, 17.6 Hz), 3.35 (1H, s) , 4.6 (2H, s), 5.58 (1H, tr, J = 8.0Hz), 6.25 (1H, d, J = 3.9Hz), 7.06 (1H, d, J = 3.9Hz), 8.9 (1H, s) , 9.30 (1H, s)
And an antibacterial agent comprising, as an active ingredient, a 5-hydroxymethyl-2-formylpyrrole derivative whose acetylated body exhibits the following physicochemical properties (1) to (9):
(1) Appearance Light colored viscous material
(2) Molecular weight (EI-MS) 264; m / z264 (M +)
(3) Molecular formula C 11 H 12 N 4 O 4
(4) Solubility in solvents: Easily soluble in ethanol and methanol, soluble in chloroform and water
(5) UV absorption spectrum (50% MeOH) 260, 295nm
(6) Red external absorption spectrum IRγmax (KBr) cm -1 : 3241, 1791, 1723, 1659, 1492, 1451, 1329, 1311, 1232, 1184, 1045, 915
(7) 1 H-NMR (CD 3 CN) ppm: δ 2.01 (3H, s), 2.76 (1H, dd, J = 6.8, 17.6 Hz), 3.09 (1H, dd, J = 9.3, 17.6 Hz) , 5.09 (2H, s), 5.42 (1H, tr, J = 8.5Hz), 6.41 (1H, d, J = 3.9Hz), 7.1 (1H, d, J = 3.9Hz), 9.08 (1H, s) , 9.39 (1H, s)
(8) 13 C-NMR (CD 3 CN) ppm: δ21.0, 38.4, 56.3, 58.3, 113.5, 126.6, 133.4, 139.7, 171.3, 175.6, 180.9
(9) Mass spectrometry GCMS (EI): 264, 263, 222, 221, 205, 193, 165, 136, 124, 108,106, 98, 79
(ａ) 外観 淡色粘稠物
(ｂ) 分子量（EI-MS） 222；m/z222(M+)
(ｃ) 分子式 C9H10N4O3
(ｄ) 溶剤に対する溶解性：エタノール、メタノールに易溶、酢酸エチル、水に可溶、クロロフォルムに難溶
(ｅ) 紫外部吸収スペクトル(MeOH) 257, 293nm
(ｆ) 赤外部吸収スペクトルIRγmax (KBr)cm-1 : 3361, 2950, 2925, 1718, 1653, 1430, 1170
(ｇ) 1H-NMR(CD3CN)ppm：δ2.73(1H,dd,J=6.8,17.6Hz), 3.07(1H,dd, J=9.3,17.6Hz), 3.35(1H,s), 4.6(2H,s), 5.58(1H,tr,J=8.0Hz), 6.25(1H,d,J= 3.9Hz), 7.06(1H,d,J=3.9Hz), 8.9(1H,s), 9.30(1H,s)
かつそのアセチル体が下記（１）〜（９）の理化学的性質を示す5-ヒドロキシメチル-2-フォルミルピロール誘導体を有効成分とする澱粉老化抑制剤。
(1) 外観 淡色粘稠物
(2) 分子量（EI-MS） 264；m/z264(M+)
(3) 分子式 C11H12N4O4
(4) 溶剤に対する溶解性：エタノール、メタノールに易溶、クロロフォルム、水に可溶
(5) 紫外部吸収スペクトル(50%MeOH) 260, 295nm
(6) 赤外部吸収スペクトルIRγmax (KBr)cm-1 : 3241, 1791, 1723, 1659, 1492, 1451, 1329, 1311, 1232, 1184, 1045, 915
(7)1H-NMR(CD3CN)ppm：δ2.01(3H,s),2.76(1H,dd,J=6.8,17.6Hz), 3.09(1H,dd,J=9.3,17.6Hz), 5.09(2H,s), 5.42(1H,tr,J=8.5Hz), 6.41(1H, d,J=3.9Hz), 7.1(1H,ｄ,J=3.9Hz), 9.08(1H,s), 9.39(1H,s)
(8) 13C-NMR(CD3CN)ppm: δ21.0, 38.4, 56.3, 58.3, 113.5, 126.6, 133.4, 139.7, 171.3, 175.6, 180.9
(9) 質量分析GCMS(EI): 264, 263, 222, 221, 205, 193, 165, 136, 124, 108,106, 98, 79 The extract obtained by extraction with a highly polar solvent from the fruit of the genus Capsicum is further purified by a process including partition extraction with ethyl acetate, chromatography using silica gel and chromatography using ODS. The following physicochemical properties (a) to (g) obtained are shown:
( a ) Appearance Light colored viscous material
( b ) Molecular weight (EI-MS) 222; m / z 222 (M +)
(C) molecular formula C 9 H 10 N 4 O 3
( d ) Solubility in solvents: Easily soluble in ethanol and methanol, soluble in ethyl acetate and water, hardly soluble in chloroform
( e ) UV absorption spectrum (MeOH) 257, 293nm
( f ) Red external absorption spectrum IRγmax (KBr) cm -1 : 3361, 2950, 2925, 1718, 1653, 1430, 1170
( g ) 1 H-NMR (CD 3 CN) ppm: δ 2.73 (1H, dd, J = 6.8, 17.6 Hz), 3.07 (1H, dd, J = 9.3, 17.6 Hz), 3.35 (1H, s) , 4.6 (2H, s), 5.58 (1H, tr, J = 8.0Hz), 6.25 (1H, d, J = 3.9Hz), 7.06 (1H, d, J = 3.9Hz), 8.9 (1H, s) , 9.30 (1H, s)
A starch aging inhibitor comprising, as an active ingredient, a 5-hydroxymethyl-2-formylpyrrole derivative, the acetyl form of which includes the following physicochemical properties (1) to (9):
(1) Appearance Light colored viscous material
(2) Molecular weight (EI-MS) 264; m / z264 (M +)
(3) Molecular formula C 11 H 12 N 4 O 4
(4) Solubility in solvents: Easily soluble in ethanol and methanol, soluble in chloroform and water
(5) UV absorption spectrum (50% MeOH) 260, 295nm
(6) Red external absorption spectrum IRγmax (KBr) cm -1 : 3241, 1791, 1723, 1659, 1492, 1451, 1329, 1311, 1232, 1184, 1045, 915
(7) 1 H-NMR (CD 3 CN) ppm: δ 2.01 (3H, s), 2.76 (1H, dd, J = 6.8, 17.6 Hz), 3.09 (1H, dd, J = 9.3, 17.6 Hz) , 5.09 (2H, s), 5.42 (1H, tr, J = 8.5Hz), 6.41 (1H, d, J = 3.9Hz), 7.1 (1H, d, J = 3.9Hz), 9.08 (1H, s) , 9.39 (1H, s)
(8) 13 C-NMR (CD 3 CN) ppm: δ21.0, 38.4, 56.3, 58.3, 113.5, 126.6, 133.4, 139.7, 171.3, 175.6, 180.9
(9) Mass spectrometry GCMS (EI): 264, 263, 222, 221, 205, 193, 165, 136, 124, 108,106, 98, 79
(ａ) 外観 淡色粘稠物
(ｂ) 分子量（EI-MS） 222；m/z222(M+)
(ｃ) 分子式 C9H10N4O3
(ｄ) 溶剤に対する溶解性：エタノール、メタノールに易溶、酢酸エチル、水に可溶、クロロフォルムに難溶
(ｅ) 紫外部吸収スペクトル(MeOH) 257, 293nm
(ｆ) 赤外部吸収スペクトルIRγmax (KBr)cm-1 : 3361, 2950, 2925, 1718, 1653, 1430, 1170
(ｇ) 1H-NMR(CD3CN)ppm：δ2.73(1H,dd,J=6.8,17.6Hz), 3.07(1H,dd, J=9.3,17.6Hz), 3.35(1H,s), 4.6(2H,s), 5.58(1H,tr,J=8.0Hz), 6.25(1H,d,J= 3.9Hz), 7.06(1H,d,J=3.9Hz), 8.9(1H,s), 9.30(1H,s)
かつそのアセチル体が下記（１）〜（９）の理化学的性質を示す5-ヒドロキシメチル-2-フォルミルピロール誘導体を有効成分とする澱粉糊化促進剤。
(1) 外観 淡色粘稠物
(2) 分子量（EI-MS） 264；m/z264(M+)
(3) 分子式 C11H12N4O4
(4) 溶剤に対する溶解性：エタノール、メタノールに易溶、クロロフォルム、水に可溶
(5) 紫外部吸収スペクトル(50%MeOH) 260, 295nm
(6) 赤外部吸収スペクトルIRγmax (KBr)cm-1 : 3241, 1791, 1723, 1659, 1492, 1451, 1329, 1311, 1232, 1184, 1045, 915
(7)1H-NMR(CD3CN)ppm：δ2.01(3H,s),2.76(1H,dd,J=6.8,17.6Hz), 3.09(1H,dd,J=9.3,17.6Hz), 5.09(2H,s), 5.42(1H,tr,J=8.5Hz), 6.41(1H, d,J=3.9Hz), 7.1(1H,ｄ,J=3.9Hz), 9.08(1H,s), 9.39(1H,s)
(8) 13C-NMR(CD3CN)ppm: δ21.0, 38.4, 56.3, 58.3, 113.5, 126.6, 133.4, 139.7, 171.3, 175.6, 180.9
(9) 質量分析GCMS(EI): 264, 263, 222, 221, 205, 193, 165, 136, 124, 108,106, 98, 79 The extract obtained by extraction with a highly polar solvent from the fruit of the genus Capsicum is further purified by a process including partition extraction with ethyl acetate, chromatography using silica gel and chromatography using ODS. The following physicochemical properties (a) to (g) obtained are shown:
( a ) Appearance Light colored viscous material
( b ) Molecular weight (EI-MS) 222; m / z 222 (M +)
(C) molecular formula C 9 H 10 N 4 O 3
( d ) Solubility in solvents: Easily soluble in ethanol and methanol, soluble in ethyl acetate and water, hardly soluble in chloroform
( e ) UV absorption spectrum (MeOH) 257, 293nm
( f ) Red external absorption spectrum IRγmax (KBr) cm -1 : 3361, 2950, 2925, 1718, 1653, 1430, 1170
( g ) 1 H-NMR (CD 3 CN) ppm: δ 2.73 (1H, dd, J = 6.8, 17.6 Hz), 3.07 (1H, dd, J = 9.3, 17.6 Hz), 3.35 (1H, s) , 4.6 (2H, s), 5.58 (1H, tr, J = 8.0Hz), 6.25 (1H, d, J = 3.9Hz), 7.06 (1H, d, J = 3.9Hz), 8.9 (1H, s) , 9.30 (1H, s)
And the starch gelatinization promoter which uses the 5-hydroxymethyl-2-formylpyrrole derivative whose acetyl body shows the physicochemical property of following (1)-(9) as an active ingredient.
(1) Appearance Light colored viscous material
(2) Molecular weight (EI-MS) 264; m / z264 (M +)
(3) Molecular formula C 11 H 12 N 4 O 4
(4) Solubility in solvents: Easily soluble in ethanol and methanol, soluble in chloroform and water
(5) UV absorption spectrum (50% MeOH) 260, 295nm
(6) Red external absorption spectrum IRγmax (KBr) cm -1 : 3241, 1791, 1723, 1659, 1492, 1451, 1329, 1311, 1232, 1184, 1045, 915
(7) 1 H-NMR (CD 3 CN) ppm: δ 2.01 (3H, s), 2.76 (1H, dd, J = 6.8, 17.6 Hz), 3.09 (1H, dd, J = 9.3, 17.6 Hz) , 5.09 (2H, s), 5.42 (1H, tr, J = 8.5Hz), 6.41 (1H, d, J = 3.9Hz), 7.1 (1H, d, J = 3.9Hz), 9.08 (1H, s) , 9.39 (1H, s)
(8) 13 C-NMR (CD 3 CN) ppm: δ21.0, 38.4, 56.3, 58.3, 113.5, 126.6, 133.4, 139.7, 171.3, 175.6, 180.9
(9) Mass spectrometry GCMS (EI): 264, 263, 222, 221, 205, 193, 165, 136, 124, 108,106, 98, 79
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| JP2002029218A JP4235389B2 (en) | 2002-02-06 | 2002-02-06 | New pyrrole derivatives |
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| JP2002029218A JP4235389B2 (en) | 2002-02-06 | 2002-02-06 | New pyrrole derivatives |
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| JP2003231676A JP2003231676A (en) | 2003-08-19 |
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| JP4235389B2 true JP4235389B2 (en) | 2009-03-11 |
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