On the Flavonoids Contained in Prunus Woods プ ル ヌ ス 属 の 材
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40(3)'58 長 谷 川:プ ル ヌ ス 属 の 材 に 含 まれ る フ ラ ボ ノ イ ド 111 On the Flavonoids Contained in Prunus Woods Masao HASEGAWA* プルヌス属の材に含まれるフラボノイ ド 長 谷 川 正 男* 要 旨 材 の 含 有 成 分,と く に フ ラ ボ ノ イ ドを と りあ げ て,こ れ を 普 通 の 化 学 的 操 作 で 取 出 し,季 節 変 化,材 中 の 分 布 を し ら べ た 。 こ れ を も と に し て プ ル ヌ ス 属 の 各sectionあ る い は 種 間 の 比 較 を し た 。 こ の 実 験 に よつ て 得 られ た 結 果 は 次 の 通 りで あ つ た 。 1.ナ リ ン ゲ ニ ン,ア ロ マ デ ン ド リ ン お よ び そ の 配 糖 体 は プ ル ヌス 属 の 材 で は 基 本 的 な 生 産 物 で あ る 。 2.プ ル ヌ ス 属 の5つ のsectionは そ れ ぞ れ 特 有 な フ ラ ボ ノ イ ドのpatternを も つ て い る 。 例 外 と し てsubsection Euprunus, Eucerasusが あ る 。 3.フ ラ ボ ノ イ ドのpatternに よ つ てsubsection Pseudocerasusは 更 に3群 に 分 け られ る。この うちの第1群 に属するものは種に特有なフラバ ノン配糖体の組合せをもつている。 4. leucoanthocyaninと フ ラバ ノ ン あ る い は フ ラ ボ ン と の 間 に は 量 的 な 拮 抗 性 が 存 在 す る 。 5.フ ラ ボ ノ イ ドの 量 は 辺 材 の 内 部 に 行 くに し た が つ て 多 くな る 。 心 材 と 辺 材 の 境 界 で 配 糖 体 とア グリコンの量比 が反対になる。 6.ピ ノ セ ム ブ リン と そ の 配 糖 体 ベ レ クン ヂ ン の 量 が 心 材 で 多 くな る こ とか ら,心 材 内 に 生 き た 柔 細 胞 が 存 在 す る こ と が 考 え られ る 。 Abstract: As a base of genetical relationship of Prunus species, the fundamental substances, flavonoids in wood are extracted by ordinary chemical procedures besides using paper chromatography. The results obtained are as follows: the quantitative change of flavonoids in concerned with the heart wood building more than the seasonal change or their localisation. The free flavonoid content in sapwood is less than the heartwood. The glycoside amounts are abundant in sapwood. The fundamental flavonoids synthesised in Prunus wood are naringenin, aroma dendrin and their glycosides. The classification of Genus Prunus according to the flavonoid pattern coincides with the taxonomical classification except the subsections Euprunus and Eucerasus. Between each flavonoid, e. g. leucoanthocyanin and flavanone or flavone there is observed an antagonism. These biochemical reactions are regulated by the gene control. I. Introduction dated. The term flavonoids used in this article Most of the flavonoids were obtained from comprises substances having the fundamental living tissues of leaves, flowers, etc., but constitution C3-C3-C6, to which flavanones, fla recently many flavonoids have been reported vones, flavonols, isoflavones, catechins and to be present in heartwood4, 5 which was leucoanthocyanidins belong. believed to consist of dead cells. The fla The flavonoids are known to be widely vonoids which accumulated in inactive cells distributed in plant tissues, and their physi of heartwood have to be regarded as physi ological role were formerly discussed by K. ologically inactive end products. How they Shibata1, R. Kuhn2 and A. Szent-Gyorgyi3, are produced there or transported from the although it could not be completely eluci tissues outside the heartwood is quite un * Government Forest Experiment Station, Meguro, Tokyo, Japan. 農林省林業試験場 112 長 谷 川:プ ル ヌ ス属 の材 に含 まれ る フ ラボ ノ イ ド 日林誌 known. From the anatomical point of view , to about 300ml. After extracting several however, through the complex reactions occ times with ether, the aqueous layer was urring in some of the wood cells, such as repeatedly extracted with ethyl acetate until wood medullary rays and wood parenchyma, the mother liqunr gave no color with magne the enzymes or enzyme systems in the cells sium powder and hydrochloric acid. take some part in the complex chemical The combined ethereal solution was evap reactions, which culminate in the production orated and the residue was divided into three of a flavonoid or flavonoids or in the transfor fractions as follows: The first fraction is the mation of a flavonoid into another. According portion soluble in hot benzene (100•`500ml.), to the theories of Beable6, of Tatum7, and of the second, the portion soluble in hot water Bonner and Zechmeister8 enzymes or enzyme (100•`500ml.), and the third, the residue, systems concerned with these biochemical which is soluble in methanol (30•`50ml.). reactions are regulated by the gene or genes. The three fractions were chromatographed From this standpoint the differentiation of end with one dimensional ascendent method. Toyo products should mean the quantitative and fi lter paper No. 3 was used throughout the qualitative, or dominant and recessive, diffe experiments and the chromatgrams were run rences of genes, as the difference of gene at room temperature. The detecting agents plays an important role in the determination were 2% methanolic ferric chloride, diazotized of species or varieties. The results obtained benzidine and ultraviolet light. by Lindstedt9, Hillis10, Marker11, Spath12 Asa Flavones, favanones. From the first fraction, hina13, and Fujita14 can be utilized in taxono the following flavonoids could be detected my. with ligroin-benzene mixture9: naringenin, Conversely, between the species which pro sakuranetin or isosakuranetin, pinocembrin, duce the same substances, there are active chrysin and tectochrysin. The results were the same enzyme systems, namely the same ascertained by utilizing three other solvent gene constitution. Accordingly, the plants systems, m-cresol: glacial acetic acid15, 60% which belong to the same genus and produce acetic acid16 and isopropyl alcohol: water16. the same constituents are related to one ano From the second fraction the following ther. fl avonoids were detected with the three sol This article reports the results of extraction vents, 60% acetic, acid, m-cresol: glacial of flavonoids from the wood of each species acetic acid: water and isopropyl alcohol: and variety of the genus Prunus, and aims at water, aromadendrin17 (katuranin), taxifolin, making some approach to the elucidation of d-catechin and l-epicatechin. the biosynthetical process of flavonoids, and From the third fraction naringenin, eriodic the chemical or genetical relations between tyol, genkwanin, luteolin, kaempferol and species and varieties or between the sections. quercetin were detectable with the previously II. Experimental described four solvent systems. Extraction of flavonoids and Ethyl acetate soluble portion was evapora chromatography ted to dryness. Part of the glucogenkwanin Wood chips (500g. to 5kg.) from the trunk and mumenin (kaempferid-7-glueoside)18 was or branch of each species and variety were obtained from the mother liquor as brown extracted in 500g. lots with two portions of precipitate. The residue was dissolved in 4l. boiling methanol, and the methanol ex 200ml. acetone, and to the acetone solution tracts were concentrated by distillation under 400•`600ml. benzene was added, when a ordinary pressure. The concentrate was then brown mass deposited, and the supernatant evaporated in a dish on a boiling water bath benzene solution was evaporated to dryness. 40(3)'58 長 谷 川:プ ル ヌ ス 属 の 材 に 含 ま れ る フ ラ ボ ノ イ ド 113 The residue was dissolved in 200ml. water. 280 mƒÊ in methanol solution, the optical den After extracting several times with ether to sity (4mg. in 50ml. methanol) being in a remove leucoanthocyanidin, the mother liquor range of 1.0 to 1.4. was mixed with an lqual volume of ethyl Extract of sap and heartwood acetate and allowed to stand for 2 weeks in constituents. an ice box. From these portions the glycosides The wood chips of Prunus speciosa prepared prunin, isosakuranin, sakuranin, verecundin19 from heartwood (600g.) and sapwood (2200g.) and equinoctin20 etc., respectively, were de were extracted separately in 300g. lots with posited. After hydrolysis, part of this frac two portions of 31. boiling methanol. The tion, the ether soluble portion was paper extracts were treated by the same method chromatographed using four solvent systems described above. The results are shown in as described above, and aromadendrin, taxi Table II. folin, eriodictyol, kaempferol and quercetin, Ratio of flavonoid contents in each respectively, were detected, so their glycosi zone of wood. des are regarded to be present in the tissues. A radial vertical section of Prunus yedoensis The Rf values of all the flavonoids detected wood (diameter, 11cm., diameter of heart in woods are given in Table III. wood, 5cm., length, 22cm.) was shaven and The substances dissolved in residual solu fi ve zones of 0.5cm. breadth were marked tion were analysed after separation of cry with pencil as shown in Figure 1. From each stals. The details of extraction works were zone 2.5g. of wood were chiseled with a given in the reports21, 22, 23. 24, 25 already publi gouge in chips. The five zones were as shed. follows: outer sapwood, middle part of sap Leucoanthocyanins. The water soluble por wood, inner sapwood, outer heartwood, and tion from the second fraction, dissolved in inner heartwood. Wood chips from each zone ether, was extracted with ether by Soxhlet's were extracted with 200ml. boiling methanol liquid percolator, Afterwards the mother for 3 hours. After evaporation of methanol, liquor was shaken many times with ethyl the residue was dissolved in 50ml.