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

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 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 , , 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 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, . 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 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. hot water. acetate and the combined extracts were eva After shaking with 150ml. ether two times, the porated to dryness. The residue and the mother liquor was shaken with 150ml. ethyl leucoanthocyanin part from ethyl acetate acetate two times. After evaporation of the solution was mixed with 2•`3 times benzene, solvent each residue was dissolved in metha and a reddish brown mass deposited on the nol, and 0.025ml. of this methanol solution bottom of the flask. The supernatant, almost was chromatographed. The concentration of colorless liquor was evaporated to dryness. each substance was roughly expressed by The reddish brown precipitate was triturated dilution number, that is, as the methanol repeatedly with acetone and benzene. The solution was diluted, the spot on the chro

pale yellow mass obtained was dissolved in matogram disappeared according to its con

a small volume of ethyl acetate. After filte centration. The volumes in ml. necessary ring a small amount of l-epicatechin, which for bringing the substance to this stage , at appeared in crystals, the mother liquor was which one spot disappeared, showed the con

evaporated to dryness. The reddish color centration of the substance . The same ex

was then removed by the acetone-benzene periment was carried out with chips of P. method. After evaporation, leucoanthocyanin verecunda wood made just in the same way . was obtained as pale yellow amorphous pow The developing agents were isopropyl al der. The absorption maximum of this crude cohol: water (22:78) and 60% acetic acid . substance obtained from various origins was The detecting agents were 2% methanolic 119 長 谷 川:プ ル ヌス属 の材 に 含 まれ る フ ラボ ノ イ ド 日林誌

ferric chloride solution , diazotized benzidine (Continued) and ultraviolet light . Toyo filter paper No. 3

was used throughout the experiments . The results are given in Table VII.

. Results and consideration

Figure 1. A. Distribution of flavonoids in Prunus wood Materials. The analysis of wood of Prunus yedoensis The name of analyzed species were as gathered from different places at different follows: seasons are given in Table I. The difference of constituents of sap and heartwood are shown in Table II. From Table I and II it is deduced that the quantitative change of fl avonoids in wood is concerned with the heartwood building more than the seasonal change or their localisation. The free fla vonoid content in sapwood is less than that in heartwood. The glycoside amounts are abundant in sapwood. From these results we should use the material which has moder ately developed heartwood for the comparison of the constituents of wood. It is difficult to obtain woods of the same growth, so the quantitative comparison of the components of each species is very difficult. From the results obtained we can compare qualitatively the components of one species with others. The woods belonging to the section Cerasus generally produce large amounts of flavano nes, flavones and isoflavones. The yield of fl avanones in the wood of the section Cerasus is the most abundant in the genus Prunus. The kinds of flavanone produced vary consi derably. We can conclude that the flavanone system in this section is completed: namely, pinocembrin (5, 7-dihydroxoyflavanone), narin genin (5 , 7 , 4'-trihydroxyflavanone), sakuranetin

III 40(3)'58 長 谷 川:プ ル ヌ ス 属 の 材 に 含 ま れ る フ ラ ボ ノ イ ド 115

(5, 4'-dihydroxy 7-methoxy flavanone), isosaku Table I (Continued) ranetin (5, 7-dihydroxy 4'-methoxyflavanone ), eriodictyol (5, 7, 3', 4'-tetrahydroxyflavanone), aromadendrin (katuranin) (5, 7, 3, 4'-tetrahydro xyflavanone), taxifolin (3, 5, 7, 3', 4'-hydro xyflavanone) and its glycoside are produced. A moderate amount of genkwanin or chrysin, Sample A was cut down at nursery of the isoflavone genistein or prunetin, and d Government Forest Experiment Station, Me catechin are found, but throughout the ex guro, Tokyo in December. The diameter periments leucoanthocyanin was not obtained of wood was 30cm and that of heartwood, from the woods belonging to this section. 26cm. Sample B was presented from the nursery This relation is represented by the next ge at Asakawa in November. Diameter was neralised formula FoFaCl, Fo, Fa, C and L 14cm. and that of heart wood, 8cm. denote flavanones, flavones, catechins and Sample C was a branch which was sent leucoanthocyanins, respectively. from Hirosaki, Aomori Prefecture, in Sep From the same standpoint the flavonoid sys tember. Diameter was 9cm. and that of heartwood, 3cm., suggesting that there tem of other sections can be represented by occurred some accurred some accident or the same generalized formula from Table IV abnormal event in the course of growth. and V which are shown as follows: Anyhow, the structure of the wood is abnor

Cerasus FoFaCl mal. Sample D was cut down at the nursery at Amygdalus foFaCL Asakawa in May. The diameter was 11cm. Prunophora FoFaCL and that of heart wood. 5cm. Padus fofaCl + confirmed by paper chromatography. Laurocerasus fofacL The capital letter shows a large amount of Table II Comparison of sap and heartwood fl avonoids and the small a less amount of constituents of Prunus speciosa fl avonoids detected by paper chromatography or color reaction26. a) Cerasus section This section was generally divided into 4 subsections, Pseudocerasus, Eucerasus, Phyllo mahaleb and Microcerasus. In these subsec tions Pseudocerasus, Eucerasus, and Phylloma haleb produce a large amount of flavanones and flavones (inclusive isoflavones). The tested species belonging to Microcerasus is (Part of the inner sapwood was lost during only Prunus tonientosa which produces no fla the preparing of wood material) vanone or flavone. Table III Table I Chromatographic data of the flavonoids in Wood constituents of Prunus yedoensis Prunus wood 116 長 谷 川:プ ル ヌス属 の 材に 合 まれ る フ ラボ ノイ ド 日林誌

Table III (Continued)

The developing agents were as follows: A, m-cresol: acetic acid: water, 24:1:25; B, isopropyl alcohol: water, 22:78; C, 60%

acetic acid; D, ligroin-benzene (15:15, %. water saturated): methanol, 30:1.

Prunus maximowiczii belonging to subsec tion Phyllomahaleb has a tendency to produce genistein and prunetin as the chief products. Prunus avium belonging to subsection Eucera sus produces genistin (genistein-7-glucoside) and prunetin as isoflavone, prunin as a fla vanone glycoside and equinoctin (chrysin-7- glucoside) as a flavone which is the chief product in this wood. There is a difference in this point, that is the lack of chrysin and its glycoside, detween Prunus avium and P. maximowiczii. There is not found any diffe rentiation between Pseudocerasus and Eucera sus except the qualitative appearance of chrysin. It can be thought that these sub section show some relationship in the ability of flavonoid synthesis. In the wood of the species belonging to the subsection Pseudocerasus are produced various kinds of flavanones. This fact is verified in Table IV and V. Genkwanin and glucogen kwanin are specific substances for this sub section. The main fiavanone glycoside and the main flavone shown by the result are characteristic of the species or the groups IV + (it is detailed afterwards). There is a very characteristic difference in this subsection,

Table Detected by paper chromatography or the color reaction. Trace below 0.01 40(3)'58 長 谷 川:プ ル ヌ ス 属 の 材 に 含 ま れ る フ ラ ボ ノ イ ド 117

namely a flavone producing capacity. Accor ding to this capacity it may be divided into 3 groups. To the first group belong genkwanin produ cing species, namely, P. jamasakura, P. speciosa, P. verecunda and P. sargentii, etc. The second group, P. nipponica, P. subhirtella, etc. has a chrysin synthesising capacity. The species in this group characteristically pro duce isoflavones, genistein and prunetin. The detectable flavanone glycoside is prunin. These characters resemble the wood of P. avium which belongs to Eucerasus. As an example of the third group P. cam panulata is worth while pointing out. The wood of this species produces a perfect fla vanone system, naringenin, aromadendrin, isosakuranetin, sakuranetin, pinocembrin, eridictyol, taxifolin, prunin (the main gly coside), sakuranin and verecundin. A trace of chrysin is found. The remarkable diffe rence of this third group from the second is that it produces no isoflavone. The first group of Pseudocerasus produces various kinds of flavanone glycosides, but the synthesizing property of the main and co occurring glycosides which are probably for med in sapwood are determined with each species. As an example of the glycoside components of wood, the author has shown in Table VI the results of analysis of P. ja masakura which was gathered from three different locations.

Table VI

It will be possible to postulate the origin

of variations belonging to the first group according to these facts. The famous varieties of "satosakura" were analysed and the following result was obtai

Tble V 118 長 谷 川:プ ル ヌ ス 属 の 材 に 合 ま れ る フ ラ ボ ノ イ ド 日林 誌

ned: yield of sakuranetin is small, so that it is

present perhaps in the sapwood as the sma

llest amount of sakuranin.

Prunus zippeliana and P. spinulosa belonging

to Laurocerasus produce naringenin, aroma

dendrin and its glycoside. All these sub

stances are found in such very small amounts Prunus speciosa produces sakuranin as a that they are detected only by paper chro main glycoside, and the yield being 2.5%. Ohwi matography25. From the wood of P. zippeliana pointed out that according to his taxonomic a trace of naringenin was obtained, and Pew29 observation the origin of the variety "sato extracted aromadendrin from the wood of sakura" is Prunus speciosa. The results of black belonging to Laurocerasus. This fl avonoid analysis agreed well with his opi section produces chiefly a pair of flavanone,

nion". The variety "yedo" resembles P. naringenin and aromadendrin, and this pair verecunda with regard to the main flavanone is the simplest flavanone in Prunus wood.

glycoside. We can think that the direction The same applies to the pine heart wood4 at

of variation should not have occurred only in which the pair of pinocembrin and pinobanksin

a way, because P. speciosa contains verecun appeared. Thus the flavanone formation of

din in heartwood. Amygdalus and Laurocerasus are very weak,

Prunus yedoensis in the most widely planted and when a comparison is made of the ability

Prunus in Japan, but the natural habitat has of flavanone synthesis between the two sec

not yet been found either in Japan or in other tions, Amygdalus seems to have developed

Asian countries. It is regarded by Ohwi as a little further than Laurocerasus.

a hybrid between P. subhirtella var. ascendens These two sections produce leucoanthocya

and P. speciosa, but the results of analysis nins, but their qualities are different; the

showed that isoflavones are produced by anthocyanidin derived from Laurocerasus

P. subhirtella but is lacking in P. yedoensis. leucoanthocyanidin indicates a purple color

So the ability of isoflavone production should when heated with methanol and hydrochloric

be referred to a recessive gene, but it is acid and an absorption maximum at 540mƒÊ.

difficult to recognize this conclusion when the On the other hand the anthocyanidin derived

result obtained by Williams28 is justifiable. from Amygdalus leucoanthocyanidin indicates

As regards the origin of this species a more a red color and an absorption maximum at

detailed study is necessary. 530mƒÊ.

(b) Amygdalus and Laurocerasus The generalized formula of the two sections

Prunus persica is the only species analysed is as follows: Amygdalus, foFaCL, Laurocera

in the section Amygdalus. This species pro sue fofacL.

duces flavanones, catechin and leucoanthocya (c) Prunophora nin. The kinds of flavanone are simpler than This section is divided into two subsections, those of Cerasus section. Naringenin, sakura Armeniaca and Euprunus and two species and

netin, aromadendrin, eriodictyol and taxifolin one variety belonging to the former subsec

were found as the free flavanone and prunin tion are analysed. These are Prunus mume, as the flavanone glycoside. The main direc P. ansu and P. mume var. microcarpa MAKINO tion of flavonoid synthesis tends to flavanone All these are indigenous plants. formation, especially naringenin and aroma From the wood of Prunus mume the follo dendrin synthesis, and additional amounts of wing flavonoids are obtained: naringenin,

eriodictyol and taxifolin are formed. The prunin, isosakuranin, mumenin, l-epicatechin 40(3)'58 長 谷 川:プ ル ヌ ス 属 の 材 に 含 ま れ る フ ラ ボ ノ イ ド 119

and leucoanthocyanin. The same kinds of which perhaps has something to do with fl avonoids are obtained from Prunus mume genetical activities. The classification accor var. microcarpa. The flavonoids obtained from ding to the generalized formula is principally P. ansu are almost the same, but as regards agreed with the taxonomical classification. fl avanones there is some difference, namely, B. Synthesis of flavonoids in wood prunin and isosakuranin are not found. In There has been published some reviews30. 31 this section the flavonol glycoside mumenin . 32. 33 on flavonoid biosynthesis, while the appeared as a specific substance contrary to authors have discussed the precursor consi the other sections. dered by Robert ROBINSON to have the follo The generalized formula is FoFaCL. wing structure: In the wood of Prunus salicina belonging to the subsection Euprunus, d-catechin and leuceanthocyanin were found. The characters of leucoanthocyanin and the anthocyanidin derived therefrom by oxidation are identical with that of Prunus mume. The generalized In the view of Scott-Moncrieff34, Price35 and formula of this section does not agree with Laurence36 the materials for synthesizing fla that of Armeniaca and it fits to fofaCL. This vonoids are used competitively in the early subsection is an exception to the section as stage. Seshadri has given data on this rela is Microcerasus to the section Cerasus. tion. Geissman and his co-workers37 postula (d) Padus ted the P factor as a regutator of dehydro The next three species of this section are xylation at 3, 4 positions in flavone and ant analysed: Prunus padus, P. ssiori and P. hocyanin skeleton. grayana. These species produce flavanones, The results obtained from analysis of fl avones, catechin, and leucoanthocyanin, and Prunus wood suggest the competitve nature only d-catechin is actually extracted. of flavonoid synthesis. In other words, the The generalized formula is fofaCl. generalized formula described above shows Now we can systematize the generalized that the amount of catechin and leucoantho formulae according to the amount ofleucoan cyanin seems not to go parallel to flavanone thocyanin. It is divided into two strains: and flavone production. The plants with large amounts of leucoanthocyanin have less amnunts of flavanone and flavone, e. g. Prunus mume and P. salicina. Between fl avones and flavanones there exists the same relation, which was observed in the const ituents of Prunus campanulata and P . misme (See Table IV and V). The production of

catechin in most cases is, however , parallel to leucoanthocyanin synthesis . This para llelism is observed in the section of Lauro This figure does not mean phylogenetical cerasus, Amygdalus and Prunophora . relationship. The author pressents this cla Heartwood has long been regarded as al ssification as an attempt to postulate the most full of dead tissues. Against this con competitive nature of the constituents in the cept there are a few, but very important wood. The formation of constituents in the comments based on microscopical observation wood is regulated by the abillity of synthesis on. one hand and physiological experi 120 長 谷 川:プ ル ヌ ス 属 の 材 に 含 ま れ る フ ラ ボ ノ イ ド 日林 誌

ments on the other. The former includes was no parallelism between the main the work of D. T. MacDougal and G. M. glycoside and the main aglycone, e. g. Smith38, who examined a very old wood of P. sargentii, P. speciosa and P. verecunda. Sequoia gigantea and found the wood paren These findings are to be well explained by chyma were alive up to the dept of about 100 the data obtained by paper chromatographic years. Among the latter is that of R. Goodwin method. The results are shown in Table VII. and D. Gooddard39. They pointed out that Table VII the heatawood pieces showed manometrically Flavonoid ratio of each zone of wood. a certain grade of respiration, though very low as compared with normal living tissues of the same species. These two observations are to be regarded as remarkable, and the author tends to the opinion that the wood parenchyma would be alive and more or less active in the physiological sense. So the fl avonoid glycosides found in Prunus wood have been synthesized from the corresponding material in sapwood. The flavanone glycosi des in woods are as follows:

* Chromatographically determined by use of 60% acetic acid. These data indicate that the kinds of fla vonoids present in each zone are almost the These glycosides are hydrolysed in the cells same, and the glycoside and its aglycone are of sapwood which grow older and older, and found to some extent in sapwood, but the the hydrolysis products should accumulate rate of the quantity present increases in gradually in inner sap and heartwood. Table heartwood. Pinocembrin and verecundin seem II shows the relation between the glycosides to be present in a rather larger amount in and its hydrolysis products. In this experi heartwood than in sapwood. From the forest ment part of the inner sapwood was lost in botanical standpoint it has been thought that the course of preparing wood materials. a particular zone exists between sap and On the other hand it is observed in the heart wood, which presents a transition zone data obtained from the ordinary extractive between these two zones. In this particular procedures that a large amount of prunin is zone glycoside-aglycone ratio changes adver found in the wood which contains a large sely, and the ability of oxidation increases amount of naringenin, e. g. in the wood of rapidly because the amount of flavone increa Prunus yedoensis and P. campanulata, and a ses to about 3 times in the wood of Prunus less amount of naringenin is found in the yedoensis. wood in which a less amount of prunin is . Summary contained, e. g. Prunus jamasakura and P. 1. Naringenin, aromadendrin and their verecunda. glycosides are fundamental products in We found some examples in which there Prunus woods.

IV 40(3)'58 長 谷 川:プ ル ヌ ス 属 の 材 に 含 ま れ る フ ラ ボ ノ イ ド 121

2. Each section of the genus Prunus has 11) R. E. MARKER, R. B. Wagner, P. R. Ulshafer, a particular favonoid pattern. The classi E. L. Wittbecker, D. P. J. Goldsmith and C. H. fi cation according to this pattern coincides Ruof: J. Am. Chem. Soc., 69, 2221 (1947). with the taxonomical classification except the 12) E. SPATH: Ber., 70 A, 83 (1937). subsections Eucerasus and Euprunus. 13) Y. ASAHINA: Acta Phytochimica 8, 33 (1934). 14) Y. FuJITA: Bot. Mag. (Tokyo), 64, 245 (1952). 3. The subsection Pseudocerasus is divided 15) E. C. BATE-SMITH: Biochem. Soc. Symposia, into 3 groups by flavone producing capability. No. 3, 62 (1950). The species belonging to the first group have 16) T. B. GAGE, C. D. Douglas and S. H. Wender: the particular flavanone glycoside. Anal. Chem., 23, 1582 (1951).

4. Between the production of leucoantho 17) W. E. HILLIS: Austral. Journ. Scient.

cyanin and fiavanone or flavone, there is Research, 5, 379 (1952).

observed an antagonism. 18) M. HASEGAWA: J. Org. Chem. in the press.

5. The flavonoid amount is largir in the 19) M. HASEGAWA and T. SHIRATO: J. Am. Chem.

inner sapwood, and glycoside and aglycon Soc., 79, 450 (1957).

forming property goes contrary in outer heart 20) M. HASEGAWA: J. Am. Chem. Soc., 79, 1783

wood as compared with sapwood. (1957).

6. There are living wood parenchyma in 21) M. HASEGAWA and T. SHIRATO: J. Am. Chem.

heartwood, which would bring about or res Soc., 74, 611 (1952). pond to the flavonoid pattern, and sometimes 22) •V: •V 76, 5559 (1957). fl avonoids may be synthesized by them, such 23) •V: •V 76, 5560 (1954).

as pinocembrin and verecundin. 24) •V: •V 77, 3557 (1955).

V. Acknowledgmenct 25) M. HASEGAWA: J. Japan. Forest. Soc., 38,

The author wishes to thank Prof. Masataka 107 (1956).

OHMASA, Prof. Shizuo HATTORI and Prof. 26) W. PIGMAN, E. ANDERSON, R. FISCHER, M. A. Fumio MAEKAWA, of the University of Tokyo, BUCHANAN and B. L. BROWING: Tappi, 36, 4

for their advice given during this investi (1933).

gation. He also appreciates very much the 27) J. OHWI: Flora of Japan, 657 (1953). collaboration of Mr. T. SHIRATO in this work. 28) A, H. WILLIAMS: Nature, 175, 213 (1955).

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