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Photopolymerizable golden-varnish in the ancient East-Asian countries, and KOSHIABURA of Japan
PROGRESS IN ORGANIC COATINGS
ELSEVIER
Progress
in Organic
Coatings
31 (1997)
81-86
Review Paper
Photopolymerizable
golden-varnish in the ancient East-Asian and KOSHIABURA of Japan
countries,
Akira Terada a,*, Y asuhiro Tanoue b, Seiji Shimamoto’ bDepartment
“Faculty of Literature, BaikBJogukuin C’nivenity, M$ji-ch6, Yoshimi. Shimorroseki, Yamaguchi 759-65, Japan of Food Science and Technology, National, Fisheries University, Nugtrtuhnnmachi, Shimonoseki, Yamaguchi 75%55, ‘Fukuoka Prefectural Yame Technical High School, Hainuzuka, Chikurgo, Fukuoka 833, Japan Received
28 June 1996; accepted
20 January
Japan
1997
Abstract Regarding the Koshiabura tree in ancient painting technology, many people have investigated its history but its material have not been made clear. KOSHIABURA was a mysterious problem among Japanese art technologists. In ancient times, it was significant that Japanese people
usually
thought
that Koshiabura,
Takanotsume
and Kakuremino
trees were
the same,
and these three
were
exactly
the trees to make
KOSHIABURA varnish for a tribute. We first reported on the chemical constituents of the KOSHIABURA varnishes made from resinous saps of Takanotsume, Japanese and Korean Kakuremino and Koshiabura trees, and found that they principally contained conjugated diyne compounds as the photopolymerizable monomers. These monomers easily polymerized under sunshine to form golden-colored, hardcoating films in a short time, and the films were waterproof and anticorrosive. In ancient times KOSHIABURA varnish in Japan was usually applied to paint armor suits, helmets, and arrowheads. The content of the diynes as the principal components were ca. 25% in Kakurcmino, 30% in Takanotsume, and 2.8% in Koshiabura saps, respectively. In addition, we have found that the acetylenes of the Kakuremino tree have strong inhibitory activities against fungi. Therefore they are phytoalexins. As already known, these kinds of conjugated diynes are in
the newest field of materials science. This paper contains general comments on the ancient photopolymerizable (KOSHIABURA varnishes in Japan) and their chemistry. 0 1997 Elsevier Science S.A. Keywords:
Ancient golden varnish; Photopolymerization;
1. Origin
of KOSHIABURA
Kakuremino
In ancient times in Japan, China, Korea and including Pohai, ‘KOSHIABURA’ (also ‘GONZETU’ by Japanese reading, JIN-QI in the present Chinese pronunciation) was used as a golden and transparent varnish for painting armor suits, helmets, and iron arrowheads for decoration and to make them golden-colored and anticorrosive. Although many old documents in these countries often refer to the name ‘golden varnish’, in Japan the real material was unknown [7,8]. The golden varnish used in ancient Japan was given lhe special name of ‘KOSHIABURA’, although its correct origin remained unproven until recently. Only Wumyo-vuiju-sho, an ancient encyclopedia of Japan, contains this term ‘KOSHIABURA’ and explains that the ‘KOSHIABURA tree was cultivated in Daishu’. Today, the Koshiabura tree * Corresponding
author.
0300-9440/97/$17.00 PII SO300-9440(97)0002
0 1997 Elsevier 1-O
Science
S.A. All rights reserved
golden
varnishes
sap; Conjugated diacetylenes
is known as Acanthopanax sciadophylloides Fr. et Sav., Araliaceae, and Daishu (Tai-Zhou) is the Linhai district in Chechiang-Sheng,China. Many years passed,and KOSHIABURA wasignored by Japanesehistorians after the Edo period. Today, KOSHIABURA hasbecomea big problem again, becauseof its newtype varnish properties containing photosensitive monomers. Terada has studied the historical documentsconcerning golden varnish from the East-Asian countries and KOSHIABURA of Japan, as well as the flora of Koshiabura and similar trees suchasKakuremino and Takanotsumeof Japanese Araliaceae plants [3,9]. It seemsthat Japanesepeople usually thought that these three trees provided the same KOSHIABURA varnish for a tribute [3]. Terada et al. investigated the chemical constituentsof the resinous sapsof these trees [l], and they concluded that KOSHIABURA varnish was called JIN-QI or HUANG-QI
82
A. Terada rt al. /Progress
in Organic
(golden or yellow varnish) in China and HOANG-CHHILI (yellow varnish) in Korea. They were the resinous saps of the Dendropanax genus, namely Dendropanax dentiger (Harms) Merr., of China [9,10], and D. morbi’ru Leb., of Korea [ 111, which belong to the same genus as the Japanese Kakuremino tree. The name ‘golden varnish’ rather than ‘yellow varnish’ was used in Japanese history [9]. However, there is no literature showing that Japanese Kakuremino sap was the same as KOSHIABURA Varnish [ 11. Recently, Terada concluded that the Chinese golden varnish tree (D. dentiger), Korean HOANG-CHHILI-namu (D. morbiferu Nakai) and Japanese Kakuremino (D. trifidus Makino) are the same by morphological observations and chemical analysis of the saps [lo,1 11. Very recently, we have concluded that the name of Daishu of Chechiang-Sheng, China, was pronounced KOSHI-NO-KUNI by the ancient Japanese, and KOSHIABURA meant ABURA (varnish) of KOSHI [12]. The traditional technique of KOSHIABURA varnish painting on armor suits and helmets in Japan may have been introduced from China through the Korean peninsula [ 131. We can theorize that Japanese Kakuremino trees growing abundantly in the western part of Japanese Islands could be easily used for the paint resources. Terada has concluded that in Japan the resinous sap of trees of Kakuremino, Takanotsume (Evodiopanax innovans Nakai), and Koshiabura were used for the same purpose to obtain KOSHIABURA varnish. The former two were major sources of the varnish, the latter was a minor source [I]. As both Takanotsume and Koshiabura are native plants to Japan, therefore their resinous saps, then KOSHIABURA varnishes, were indigenous varnishes of Japan. These unique Japanese resin trees provided large amounts of the valuable KOSHIABURA varnish. These special circumstances comprise the difference between Japanese KOSHIABURA varnish and Chinese JIN-QI, HUANG-QI or Korean HOANG-CHHILI. We have found that all the resinous saps mentioned here contained aliphatic conjugated diyne compounds of C17-Cis as their principles, and these acetylenes easily photopolymerized under sunshine within about 30 min, resulting in the formation of golden-colored and hard coating films, insoluble in solvents and infusible. These characteristics brought ‘photosensitive polymerization ability’ to this ancient golden varnish ‘KOSHIABURA’; Yasuda [4] reported in 1928 that in Korea the painters used ‘HOANG-CHHILI’ to paint on wooden cabinets under sunshine irradiation under the open sky.
2. KOSHIABURA-painted
articles in history
The varnish was so precious that it to the Imperial Courts of China from time of the Tang Dynasty. Today, we made from KOSHIABURA varnish
was brought as tributes Japan and Korea in the have no distinct article remaining, except ‘ten
Coatings
31 (1997)
81-86
knives in clustered sheath’ in the Shoso-in national treasure. This treasure contains two articles. The literature says they are ‘small files’ painted with KOSHIABURA varnish. This fact is authenticated by Todaiji-Kenmotswcho (a list of the treasures dedicated by the Empress Komyo to Todai-ji temple). However, the material of KOSHIABIJRA is not as yet identified in detail, because the painted parts are not the typical golden color of KOSHIABURA varnish, but are black [ 151. Like this discovery, the KOSHIABURA-painted article of antiquity will be rare in Japan, and also in other countries, since the age of KOSHIABURA utilization was relatively ancient times.
3. Sap harvesting
and KOSHIABURA
painting
Kakuremino and Takanotsume trees secrete resinous sap from the plants when the bark is cut. Kakuremino and Takanotsume saps run easily in the summer season. The Koshiabura tree gives only a little sap during winter [9]. In general, sap consists of water, gum and oil, and usually obtained as a light-yellow emulsion, but the color gradually changes into a yellow-brown with aging. After filtration, the sap can be applied to paint wooden articles and paper fans, etc., similar to using a modern varnish of water-emulsion type. The painted articles easily dry under sunshine. In Korea, until 1928, people used to coat paper fans and wooden cabinets with HOANG-CHHILI varnish but the tee hnique was secret and therefore is not known clearly today [14]. Films made from KOSHIABURA varnish are light-yehow of golden color and transparent, and as hard as Japanese lacquer and polyester varnish films (8H in a pencil scratch test). The adhesion property of KOSHIABURA varnish judged by JIS-K 5400 was not so high, about 4 on a ferrotype plate [2 I.
4. Conjugated Takanotsume
diyne compound from the resinous sap of tree (Evodiopnnax innovans nakai) [4]
Here, we deal with detection of a diyne compound ((-I(Z)-1,9-heptadecadiene-4,6-diyne-3-01) in Takanotume sap and its polymerization in sunlight (also see Section 7). 4.1. Separation and identijcation
[4]
The ethanolic extract of the sap was a red-brown oil, and showed conjugated diyne absorption bands in IR and UV which implied an ene-diyne conjugated syslem [ 161. Since this sample accompanied many mono- and sesqui-terpenes and polymers and was very labile, catalytic hydrogenation at ordinary temperature and pressure was carried out an.d gave white crystals: C17H360, in 27% yield from sap. ‘“CNMR and other analytical evidence showed that this was 3heptadecanol. After TLC separation and purification of the above ethanolic extract, a diyne, CnH140 was obtained in 29% yield,
A. Terada et al. /Progress
in Organic
which showed [cY];’ -36.93”; the IR spectrum was identical to that of (-)-(Z)-1,9-heptadecadiene-4,6-diyne-3-01 (I), panaxynol, previously isolated and identified by Takahashi et al. [17-201 from the Ginseng root (Panax ginseng C.A. Meyer) in 0.1% yield. This was also identical with the carrotatoxin isolated in trace amount (between 10 and 20 ppm) as a natural toxicant from vegetable carrot (Daucus carota L.) by Crosby and Aharonson [21], and with falcarinol from Fulcalia uulgaris Bemh and from many other Umbelliferae by Bohlmann et al. [22].
5. Conjugated diyne compounds from the resinous sap of Japanese kakuremino (Dendropanax trijdus Makino)
151 As the principal components of Kakuremino-KOSHIABURA, two conjugated diacetylenic compounds, (9Z,16E)9,16-octadecadiene-12,14-diynoic acid (II) and (--)-(Z)-16hydroxy-9,17-octadecadiene12,14-diynal (III) were isolated for the first time. Also (-)-(Z)-9,17-octadecadiene12,14-diyne-1,16-dial (IV) and (-)-(Z)-16-hydroxy-9,17octadecadiene- 12,lCdiynoic acid methyl ester (V) were obtained in great quantities. The resinous sap of the Kakuremino tree (Dendropanux genus) was the common KOSHIABURA varnish in the old East-Asian countries.
Coatings
31 (1997)
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83
the free acid of V in 0.034% and 0.23% yields, respectively, from fresh leaves of D. tri$dus Makino as colorless oils by ethyl acetate extraction. 5.2. (9Z,16E)-9,16-Octadecadiene-12,14-diynoic
acid (II)
Fraction l-2 of Table 1 gave crystals (330 mg). Repeated recrystallizations from hexane gave white crystals of m.p. 50.5-52°C. The IR spectrum shows the C = C at 2225, 2120, and the tram CH=CH at 950 cm -‘, absorption peaks of -C=C-(C = C),- structure are in UV (Fig. 4) [16], and mol. wt. is 272 at MS. Further detailed data of IR, MS, ‘H- and 13C-NMR, and C, H, N analysis support the structure of II (C18H240z, m/z 272). For compound II, white crystals gradually changed into yellow, surface-melted, and polymerized to form a yellow solid mass at room temperature. 5.2.1. Catalytic hydrogenation of II A sample of II (192 mg) in ethanol (10 ml) was hydrogenated in the presence of Willstztter’s platinum black catalyst (44 mg) at normal pressure and temperature, and 5.6 M amounts of hydrogen were absorbed, giving an authentic sample of stearic acid (89%), m.p. 68.5-70°C. 5.3. (-)-(Z}-16Hydroxy-9,I (Irl) I-51
7-octadecadiene-,12,14
diynal
5.1. Separation [5] A methanol extract of fresh sap from a Japanese Kakuremino on silica-gel column chromatography gave four main fractions of diyne compounds of 18 carbon atoms as follows. CH,CH=CH-(C=C)&H2CH=CH(CH,),COOH E
(II)
(6.4% yield)
Z
CH,=CH-CH(OH)(C=C),CH2CH=CH=CH(CH&COH
(III)
(1.9% yield)
Z
CH,=CH-CH(OH)(C=C),CH2CH=CH=CH(CH~)sOH
(TV)
(4.7% yield)
Fraction 2-l of Table 2 was confirmed to be the aldehyde III by the following analyses. The IR spectrum shows strong absorption bands of aldehyde at 2720 and 1720 cm-‘, -(C-C),structure is in UV (Fig. 4) [16], and the NMR spectrum showed almost the same pattern as that of panaxynol from the sap of the Takanotsume tree. Mol. wt. was 272 (M+) and optical rotation was minus, [cy]$/ -25.0”. These (-)-(Z)-16-hydroxy-9,17+ctadecadienedata indicated 12,14-diynal (III). All the data, IR, UV, ‘H-NMR and MS (m/z 272) support the structure of III.
Z
CH,=CH-CH(OH)(CS),CH~CH=CH(CH&COOCH~
(V)
(2.3% yield)
Z
The reason for the occurrence of the methyl ester V was that during the chromatographic separation using silica-gel, IV and the free acid of V were eluted at the same time, so that the mixture was chromatographed again using an acidwashed alumina and IV was obtained as the first elute and free acid of V was the remainder. During the elution of the remainder by HCl-acidic methanol the methyl ester (V) was formed. Compounds II and III were new compounds isolated for the first time here [5]. Compound II was a presumed intermediate of the biological process shown by Bohlmann et al., as the sequence from crepenynic acid by the plant-enzymatic dehydrogenation [23]. Kawazu et al. [24] had already isolated the diol IV and
5.4. The absolute conjiguration of 16OH of (-)-(Z)-16hydroxy-9,17-octadecadiene-12,14-diynal (III) I.51 Further we emphasize that III, IV, and V obtained here were all laevo-rotatory; the absolute configurations of 16OH in III, IV and V should be R according to Kawazu et al. Table
1
Isolation
of polyacetylenes
from Japanese Kakuremino
Fraction
Yield
l-1 l-2 1-3 l-4
513 330 31 11
Total
885 (99)
(mg (%)) (58) (37) (3) (1)
Form
sap and color
Viscous orange-red oil Light yellow crystals Viscous orange-red oil Viscow orange-red oil
A. Terada
84
et al. /Progress
in Organic
Coatings
31 (1997)
81-86
6. Conjugated diyne compounds from the resinous sap of the Koshiahura tree (Acanthopanax sciadophylloides Fr. et Sav.) [6] (-)-(~-16-Hydroxy-9,17-octadecadiene-12,14-diyne-l-ylformate (VI) and (-)-(2)9,17-octadecadiene-12,14-diynel,l&diol (IV) were isolated from the sap. These acetylenic compounds were the principal components of the Japanese golden varnish, KOSHIABURA, of ancient times.
hv
a
b
6. I. Separation --CHz\ R
:
~CHzhW
,c=c, H -
R’:
-CH,\
_
~CH&COOH
F-C\ H
H
CHCH=CHz -,c=c; H
A,,
H -
,c=c, H
CH,
-CH,\
_
H
R’ : -CHCH=CH2 I OH
-
Fig. 1. Isolated
-CHz\
Acid
monomers
_ /c-c\ H
H
CHCH=CHp I OH
Iv
H
III
!CH&COOH
/c-c\ H
jCH,),CHO
CHCH=CHp I OH
II
~WWH
--CHz\ :
_ F-T H
H
I
R
-CH,\
-
jCH&qH 0 H
CHCH=CHp OH VI
of V
6.2. (-)-(Z}-9,17-octadecadiene-12,14-diyne-1,16-dio1
and their photopolymerizations.
[24]. They had obtained such conclusions by applications of Brewster’s rule [24]. 5.5. Kakuremino
A methanol extract of the sap was washed with hexane to remove the accompanying terpene hydrocarbons and a yellow oil remained (13.6%). TLC separation of this oil gave the results shown in Table 3. From fraction 3-3 of Table 3, (-)-(2)-9,1’7octadecadiene12,14-diyne- 1, I6-diol (IV) was obtained as a chromatographically pure sample in a yield of 2.0% after further purification by preparative liquid chromatography. The IR spectrum of IV was identical to that of an authentic sample (see Section 5.1). Fraction 3-6 gave (-)-(Z)- 16-hydroxy-9,17-octadecadiene- 12,1Cdiyne-I -yl-formate (VI).
sup acetylenes as phytoalexin
Kawazu et al. [24] also had found that IV and the free acid of V showed prefect inhibition against condium germination of Cochliobolus miyabeanus. Terada et al. found that these acetylenic compounds were much more effective to Trichophyton mentagrophytes, a fungus of water-eczema, compared with a commercial drug [25]. Therefore we suggest that these diacetylenic compounds should be phytoalexin. obtained when the tree-bark was cut.
(IV)
From fraction 3-3 of Table 3, an analytical sample (30 mg) of IV was obtained after purification using preparative liquid chromatography. The IR, UV and ‘H-NMR spectra were identical to those of (-)-(Z)-9,17-octadecadiene-12,1,4-cliyne-1,16-diol obtained already from the sap of the Kakuremino tree (Dendropanax trijdus Makino) (see Section fi.1). This sample (IV) showed [cY]~ -48.9”. 6.3. (-)-(Z)-l6-Hydroxy-9,17-octadecadiene-12,14-diyneI-yl-formate (VI) [6] From fraction 3-6 (51 mg) of Table 3, an ianalytical sample (13 mg) of VI was obtained as the main fraction from Table 3 TLC Separation of the yellow bura tree (see Section 7.1)
Table 2 Further
chromatographic
separation
of fraction
Fraction
Solvent
Yield
2-l 2-2 2-3 2-4 2-s
CHCl? 30% Et,0 in CHClj 20% MeOH in Et20 MeOH 1% HCl in MeOH
98 (20) 192 (39) 132 (27)
(mg (%))
28 (6) 41 (8)”
Form
1
Fraction
Rf
and color
3-1 3-2 3-3 3-4 3-5 3-6 3-7 3-8
co.07 0.07-0.27 0.2,7AI.45 0.455033 0.53-0.77 0.77-0.87 0.874.92 0.92-I .OO
Pale-yellow Brown oil Brown oil Brown oil Brown oil
oil
g) from resinous
sap of Koshia-
-
Yield 26 46 40 10 23 51 14 18
(mg (%)) (6.6) (1 1.7) (10.2) (2.5) (5.8) (13.0) (3s) (4.6)
491 (100)
Total “This amount
1-1 of Table
oil (0.392
means the yield of V
Total
-
228 (57.9)
A. Teruda
et al. /Progress
in Organic
Coatings
31 (1997)
81-86
85
I - Monomfw
,.,I, 200
300
250 Wavelength
I nm
Fig. 4. UV spectra of monomers Wavenumber
Fig. 2. IR spectra of monomers Takanotsume sap.
I, II (in KBr),
III, and polymers
of I and
liquid chromatographic purification. This sample showed [cx]~ -19.2”. This showed 1720 (C=O), 1180 cm-’ (HC(=zO)-OR), and lack of the -CH20H alcoholic absorption of IV at 1050 cm-’ in the IR. The ‘H NMR spectrum showed at 6 8.06 (s, lH, -CH20CHO). All other spectral data were almost the same as those for diol IV. MS: mol. wt. 302 (M+) agreed with the molecular weight of a mono-ester of IV and formic acid. Again, the methanolysis in the presence of a catalytic amount of sulfuric acid gave diol IV. Therefore, here we obtained a 13% yield of (-)-(Z)-16-hydroxy9,17-octadecadiene-12,14-diyne-1-yl-formate (VI). This gradually decomposed to give diol IV on storage. preparative
7. The characterizations [41
of conjugated
diyne polymers
In general, a conjugated diyne compound (Fig. 1, I-VI) quickly polymerizes under daylight [26] or UV-light irra-
-
II and 111.
I cm-’
Monomer
(I) (6.34 X iO-5 mol dm’3 in ethanol)
Polymer
film of I. on silica-glass
diation [27], and the polymer structure, like b in Fig. 1 for example, may be typical in the case of the co.njugated diyne [4]. Upon polymerization, the carbon-carbon double bonds in the R and R’ groups of I-VI may be co-operative during polymerization. The IR and UV absorption spectra of the dried film are shown in Figs 2-4, along with those of I, II and III. The IR-absorption bands of the monomer I at 2255 (C-C-C-C, strong), 983 and 929 (vinyl), and 692 cm-’ (C=C cis) were absent in the polymer film (Fig. 2). Moreover, new characteristic bands of the polymer of I appeared at 2195,2155, and 2120 (C-C-C=C, conjugated, all weak), and at 979 and 955 cm-’ (C=C, conjugated). Tieke et al. ascribed these phenomena to the C=C- streching modes of the polymer backbone with various C-C skeleton motions, judging from the large number of small peaks around them [28]. In addition, the structure of the polymer was supported by the finding of Baughman et al. that the polymer backbone was represented by (=C-C-C-C=),, from its Raman spectra [29]. These facts show that the polymer backbone is built up from a structure like b in Fig. 1. The UV spectrum of the polymer (Fig. 3) shows a bathochromic shift and the polymer color is, therefore, a goldenyellow. Usually, to make Langmuir-Blodgett multilayers, a
plate
0
500 Wavelength
Wavelength
Fig. 3. UV spectra of monomer
/ nm
I and its polymer.
600 I “m
Fig. 5. Fluorescence spectra of (KOSHIABURA) nm). (By courtesy of Mr Y. Matsuda.)
films (excited by UV (365
86
A. Terada
et al. /Progress
in Organic
number of conjugated diacetylenes are employed in solid state polymerization by irradiation of the UV light from a high-pressure mercury lamp; the reactions come to completion within a few minutes. These polymerizations proceed topochemically without any destruction of the layer structures, and appear as deep purple; this color changes irreversibly to red upon treatment with ethanol or chloroform. Because the net-worked insoluble polymer (b in Fig. l), which Terada et al. obtained here, is not such a high-molecular-weight polymer and does not have such a stereoregularity, it therefore shows a golden-yellow color owing to the short-distance conjugation of carbon-carbon double and triple bonds in the polymer backbone. Krieger reported that a polymer with a highly planar backbone is blue, that a slightly planar one is red, and that a highly non-planar one is yellow [30]. We also show the IR spectrum of a dried film (Fig. 2) of Takanotsume sap. This is almost the same as that of polymer I (Fig. 2). Fig. 5 shows the fluorescent spectra of the polymer films, dried film of sap of Japanese Kakuremino, and the spectrum of a Korean dish painted with Korean yellow varnish. All of them have their peaks at similar positions (ca. 530 nm). As these polymers have such a yellow appearance by the fluorescent-yellow emission, the golden color of the coating films will be emphasized greatly under sunshine UV.
Coatings
[6] A. Terada, Abstracts
Abstracts of the LVIII Biannual Meeting Japan, Tokyo, 1989, No. 1M 41.
of the Chemical
Society
of
Y. Tanoue of the LIX
and S. Shimamoto, Biannual
Meeting
Partially of the
Tokyo, 1990, No. IC6 17, p. 1167. Matsui, Sci. Anriq., 22 (1978) 48. Matsui, Sci. Antiq., 26 (1981) 15. Terada, Kagakushi Kenkyu (J. Hisi. Sci. Jpn.) Terada, Kagakushi Kenkyu (J. Hist. Sci. Jpn.) Terada, Ronshu (Discussions) of Baik6jogakuin
[71 E. PI E. 191 A. [lOI A. Cl11 A. 42. [I21 A. Terada, Ronshu 12. [I31 M. Suenaga, Nippon of Japan).
Sogen-sha Cl41 K. Yasuda, Reports
[I51 [I61 [I71 Cl81 [I91 [201 [211 [221 1231 ~241
[26] [27]
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81-86
presented
Chemical
to the
Society
of
lapan,
~251
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ELSEVIER
Progress
in Organic
Coatings
31 (1997)
81-86
Review Paper
Photopolymerizable
golden-varnish in the ancient East-Asian and KOSHIABURA of Japan
countries,
Akira Terada a,*, Y asuhiro Tanoue b, Seiji Shimamoto’ bDepartment
“Faculty of Literature, BaikBJogukuin C’nivenity, M$ji-ch6, Yoshimi. Shimorroseki, Yamaguchi 759-65, Japan of Food Science and Technology, National, Fisheries University, Nugtrtuhnnmachi, Shimonoseki, Yamaguchi 75%55, ‘Fukuoka Prefectural Yame Technical High School, Hainuzuka, Chikurgo, Fukuoka 833, Japan Received
28 June 1996; accepted
20 January
Japan
1997
Abstract Regarding the Koshiabura tree in ancient painting technology, many people have investigated its history but its material have not been made clear. KOSHIABURA was a mysterious problem among Japanese art technologists. In ancient times, it was significant that Japanese people
usually
thought
that Koshiabura,
Takanotsume
and Kakuremino
trees were
the same,
and these three
were
exactly
the trees to make
KOSHIABURA varnish for a tribute. We first reported on the chemical constituents of the KOSHIABURA varnishes made from resinous saps of Takanotsume, Japanese and Korean Kakuremino and Koshiabura trees, and found that they principally contained conjugated diyne compounds as the photopolymerizable monomers. These monomers easily polymerized under sunshine to form golden-colored, hardcoating films in a short time, and the films were waterproof and anticorrosive. In ancient times KOSHIABURA varnish in Japan was usually applied to paint armor suits, helmets, and arrowheads. The content of the diynes as the principal components were ca. 25% in Kakurcmino, 30% in Takanotsume, and 2.8% in Koshiabura saps, respectively. In addition, we have found that the acetylenes of the Kakuremino tree have strong inhibitory activities against fungi. Therefore they are phytoalexins. As already known, these kinds of conjugated diynes are in
the newest field of materials science. This paper contains general comments on the ancient photopolymerizable (KOSHIABURA varnishes in Japan) and their chemistry. 0 1997 Elsevier Science S.A. Keywords:
Ancient golden varnish; Photopolymerization;
1. Origin
of KOSHIABURA
Kakuremino
In ancient times in Japan, China, Korea and including Pohai, ‘KOSHIABURA’ (also ‘GONZETU’ by Japanese reading, JIN-QI in the present Chinese pronunciation) was used as a golden and transparent varnish for painting armor suits, helmets, and iron arrowheads for decoration and to make them golden-colored and anticorrosive. Although many old documents in these countries often refer to the name ‘golden varnish’, in Japan the real material was unknown [7,8]. The golden varnish used in ancient Japan was given lhe special name of ‘KOSHIABURA’, although its correct origin remained unproven until recently. Only Wumyo-vuiju-sho, an ancient encyclopedia of Japan, contains this term ‘KOSHIABURA’ and explains that the ‘KOSHIABURA tree was cultivated in Daishu’. Today, the Koshiabura tree * Corresponding
author.
0300-9440/97/$17.00 PII SO300-9440(97)0002
0 1997 Elsevier 1-O
Science
S.A. All rights reserved
golden
varnishes
sap; Conjugated diacetylenes
is known as Acanthopanax sciadophylloides Fr. et Sav., Araliaceae, and Daishu (Tai-Zhou) is the Linhai district in Chechiang-Sheng,China. Many years passed,and KOSHIABURA wasignored by Japanesehistorians after the Edo period. Today, KOSHIABURA hasbecomea big problem again, becauseof its newtype varnish properties containing photosensitive monomers. Terada has studied the historical documentsconcerning golden varnish from the East-Asian countries and KOSHIABURA of Japan, as well as the flora of Koshiabura and similar trees suchasKakuremino and Takanotsumeof Japanese Araliaceae plants [3,9]. It seemsthat Japanesepeople usually thought that these three trees provided the same KOSHIABURA varnish for a tribute [3]. Terada et al. investigated the chemical constituentsof the resinous sapsof these trees [l], and they concluded that KOSHIABURA varnish was called JIN-QI or HUANG-QI
82
A. Terada rt al. /Progress
in Organic
(golden or yellow varnish) in China and HOANG-CHHILI (yellow varnish) in Korea. They were the resinous saps of the Dendropanax genus, namely Dendropanax dentiger (Harms) Merr., of China [9,10], and D. morbi’ru Leb., of Korea [ 111, which belong to the same genus as the Japanese Kakuremino tree. The name ‘golden varnish’ rather than ‘yellow varnish’ was used in Japanese history [9]. However, there is no literature showing that Japanese Kakuremino sap was the same as KOSHIABURA Varnish [ 11. Recently, Terada concluded that the Chinese golden varnish tree (D. dentiger), Korean HOANG-CHHILI-namu (D. morbiferu Nakai) and Japanese Kakuremino (D. trifidus Makino) are the same by morphological observations and chemical analysis of the saps [lo,1 11. Very recently, we have concluded that the name of Daishu of Chechiang-Sheng, China, was pronounced KOSHI-NO-KUNI by the ancient Japanese, and KOSHIABURA meant ABURA (varnish) of KOSHI [12]. The traditional technique of KOSHIABURA varnish painting on armor suits and helmets in Japan may have been introduced from China through the Korean peninsula [ 131. We can theorize that Japanese Kakuremino trees growing abundantly in the western part of Japanese Islands could be easily used for the paint resources. Terada has concluded that in Japan the resinous sap of trees of Kakuremino, Takanotsume (Evodiopanax innovans Nakai), and Koshiabura were used for the same purpose to obtain KOSHIABURA varnish. The former two were major sources of the varnish, the latter was a minor source [I]. As both Takanotsume and Koshiabura are native plants to Japan, therefore their resinous saps, then KOSHIABURA varnishes, were indigenous varnishes of Japan. These unique Japanese resin trees provided large amounts of the valuable KOSHIABURA varnish. These special circumstances comprise the difference between Japanese KOSHIABURA varnish and Chinese JIN-QI, HUANG-QI or Korean HOANG-CHHILI. We have found that all the resinous saps mentioned here contained aliphatic conjugated diyne compounds of C17-Cis as their principles, and these acetylenes easily photopolymerized under sunshine within about 30 min, resulting in the formation of golden-colored and hard coating films, insoluble in solvents and infusible. These characteristics brought ‘photosensitive polymerization ability’ to this ancient golden varnish ‘KOSHIABURA’; Yasuda [4] reported in 1928 that in Korea the painters used ‘HOANG-CHHILI’ to paint on wooden cabinets under sunshine irradiation under the open sky.
2. KOSHIABURA-painted
articles in history
The varnish was so precious that it to the Imperial Courts of China from time of the Tang Dynasty. Today, we made from KOSHIABURA varnish
was brought as tributes Japan and Korea in the have no distinct article remaining, except ‘ten
Coatings
31 (1997)
81-86
knives in clustered sheath’ in the Shoso-in national treasure. This treasure contains two articles. The literature says they are ‘small files’ painted with KOSHIABURA varnish. This fact is authenticated by Todaiji-Kenmotswcho (a list of the treasures dedicated by the Empress Komyo to Todai-ji temple). However, the material of KOSHIABIJRA is not as yet identified in detail, because the painted parts are not the typical golden color of KOSHIABURA varnish, but are black [ 151. Like this discovery, the KOSHIABURA-painted article of antiquity will be rare in Japan, and also in other countries, since the age of KOSHIABURA utilization was relatively ancient times.
3. Sap harvesting
and KOSHIABURA
painting
Kakuremino and Takanotsume trees secrete resinous sap from the plants when the bark is cut. Kakuremino and Takanotsume saps run easily in the summer season. The Koshiabura tree gives only a little sap during winter [9]. In general, sap consists of water, gum and oil, and usually obtained as a light-yellow emulsion, but the color gradually changes into a yellow-brown with aging. After filtration, the sap can be applied to paint wooden articles and paper fans, etc., similar to using a modern varnish of water-emulsion type. The painted articles easily dry under sunshine. In Korea, until 1928, people used to coat paper fans and wooden cabinets with HOANG-CHHILI varnish but the tee hnique was secret and therefore is not known clearly today [14]. Films made from KOSHIABURA varnish are light-yehow of golden color and transparent, and as hard as Japanese lacquer and polyester varnish films (8H in a pencil scratch test). The adhesion property of KOSHIABURA varnish judged by JIS-K 5400 was not so high, about 4 on a ferrotype plate [2 I.
4. Conjugated Takanotsume
diyne compound from the resinous sap of tree (Evodiopnnax innovans nakai) [4]
Here, we deal with detection of a diyne compound ((-I(Z)-1,9-heptadecadiene-4,6-diyne-3-01) in Takanotume sap and its polymerization in sunlight (also see Section 7). 4.1. Separation and identijcation
[4]
The ethanolic extract of the sap was a red-brown oil, and showed conjugated diyne absorption bands in IR and UV which implied an ene-diyne conjugated syslem [ 161. Since this sample accompanied many mono- and sesqui-terpenes and polymers and was very labile, catalytic hydrogenation at ordinary temperature and pressure was carried out an.d gave white crystals: C17H360, in 27% yield from sap. ‘“CNMR and other analytical evidence showed that this was 3heptadecanol. After TLC separation and purification of the above ethanolic extract, a diyne, CnH140 was obtained in 29% yield,
A. Terada et al. /Progress
in Organic
which showed [cY];’ -36.93”; the IR spectrum was identical to that of (-)-(Z)-1,9-heptadecadiene-4,6-diyne-3-01 (I), panaxynol, previously isolated and identified by Takahashi et al. [17-201 from the Ginseng root (Panax ginseng C.A. Meyer) in 0.1% yield. This was also identical with the carrotatoxin isolated in trace amount (between 10 and 20 ppm) as a natural toxicant from vegetable carrot (Daucus carota L.) by Crosby and Aharonson [21], and with falcarinol from Fulcalia uulgaris Bemh and from many other Umbelliferae by Bohlmann et al. [22].
5. Conjugated diyne compounds from the resinous sap of Japanese kakuremino (Dendropanax trijdus Makino)
151 As the principal components of Kakuremino-KOSHIABURA, two conjugated diacetylenic compounds, (9Z,16E)9,16-octadecadiene-12,14-diynoic acid (II) and (--)-(Z)-16hydroxy-9,17-octadecadiene12,14-diynal (III) were isolated for the first time. Also (-)-(Z)-9,17-octadecadiene12,14-diyne-1,16-dial (IV) and (-)-(Z)-16-hydroxy-9,17octadecadiene- 12,lCdiynoic acid methyl ester (V) were obtained in great quantities. The resinous sap of the Kakuremino tree (Dendropanux genus) was the common KOSHIABURA varnish in the old East-Asian countries.
Coatings
31 (1997)
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83
the free acid of V in 0.034% and 0.23% yields, respectively, from fresh leaves of D. tri$dus Makino as colorless oils by ethyl acetate extraction. 5.2. (9Z,16E)-9,16-Octadecadiene-12,14-diynoic
acid (II)
Fraction l-2 of Table 1 gave crystals (330 mg). Repeated recrystallizations from hexane gave white crystals of m.p. 50.5-52°C. The IR spectrum shows the C = C at 2225, 2120, and the tram CH=CH at 950 cm -‘, absorption peaks of -C=C-(C = C),- structure are in UV (Fig. 4) [16], and mol. wt. is 272 at MS. Further detailed data of IR, MS, ‘H- and 13C-NMR, and C, H, N analysis support the structure of II (C18H240z, m/z 272). For compound II, white crystals gradually changed into yellow, surface-melted, and polymerized to form a yellow solid mass at room temperature. 5.2.1. Catalytic hydrogenation of II A sample of II (192 mg) in ethanol (10 ml) was hydrogenated in the presence of Willstztter’s platinum black catalyst (44 mg) at normal pressure and temperature, and 5.6 M amounts of hydrogen were absorbed, giving an authentic sample of stearic acid (89%), m.p. 68.5-70°C. 5.3. (-)-(Z}-16Hydroxy-9,I (Irl) I-51
7-octadecadiene-,12,14
diynal
5.1. Separation [5] A methanol extract of fresh sap from a Japanese Kakuremino on silica-gel column chromatography gave four main fractions of diyne compounds of 18 carbon atoms as follows. CH,CH=CH-(C=C)&H2CH=CH(CH,),COOH E
(II)
(6.4% yield)
Z
CH,=CH-CH(OH)(C=C),CH2CH=CH=CH(CH&COH
(III)
(1.9% yield)
Z
CH,=CH-CH(OH)(C=C),CH2CH=CH=CH(CH~)sOH
(TV)
(4.7% yield)
Fraction 2-l of Table 2 was confirmed to be the aldehyde III by the following analyses. The IR spectrum shows strong absorption bands of aldehyde at 2720 and 1720 cm-‘, -(C-C),structure is in UV (Fig. 4) [16], and the NMR spectrum showed almost the same pattern as that of panaxynol from the sap of the Takanotsume tree. Mol. wt. was 272 (M+) and optical rotation was minus, [cy]$/ -25.0”. These (-)-(Z)-16-hydroxy-9,17+ctadecadienedata indicated 12,14-diynal (III). All the data, IR, UV, ‘H-NMR and MS (m/z 272) support the structure of III.
Z
CH,=CH-CH(OH)(CS),CH~CH=CH(CH&COOCH~
(V)
(2.3% yield)
Z
The reason for the occurrence of the methyl ester V was that during the chromatographic separation using silica-gel, IV and the free acid of V were eluted at the same time, so that the mixture was chromatographed again using an acidwashed alumina and IV was obtained as the first elute and free acid of V was the remainder. During the elution of the remainder by HCl-acidic methanol the methyl ester (V) was formed. Compounds II and III were new compounds isolated for the first time here [5]. Compound II was a presumed intermediate of the biological process shown by Bohlmann et al., as the sequence from crepenynic acid by the plant-enzymatic dehydrogenation [23]. Kawazu et al. [24] had already isolated the diol IV and
5.4. The absolute conjiguration of 16OH of (-)-(Z)-16hydroxy-9,17-octadecadiene-12,14-diynal (III) I.51 Further we emphasize that III, IV, and V obtained here were all laevo-rotatory; the absolute configurations of 16OH in III, IV and V should be R according to Kawazu et al. Table
1
Isolation
of polyacetylenes
from Japanese Kakuremino
Fraction
Yield
l-1 l-2 1-3 l-4
513 330 31 11
Total
885 (99)
(mg (%)) (58) (37) (3) (1)
Form
sap and color
Viscous orange-red oil Light yellow crystals Viscous orange-red oil Viscow orange-red oil
A. Terada
84
et al. /Progress
in Organic
Coatings
31 (1997)
81-86
6. Conjugated diyne compounds from the resinous sap of the Koshiahura tree (Acanthopanax sciadophylloides Fr. et Sav.) [6] (-)-(~-16-Hydroxy-9,17-octadecadiene-12,14-diyne-l-ylformate (VI) and (-)-(2)9,17-octadecadiene-12,14-diynel,l&diol (IV) were isolated from the sap. These acetylenic compounds were the principal components of the Japanese golden varnish, KOSHIABURA, of ancient times.
hv
a
b
6. I. Separation --CHz\ R
:
~CHzhW
,c=c, H -
R’:
-CH,\
_
~CH&COOH
F-C\ H
H
CHCH=CHz -,c=c; H
A,,
H -
,c=c, H
CH,
-CH,\
_
H
R’ : -CHCH=CH2 I OH
-
Fig. 1. Isolated
-CHz\
Acid
monomers
_ /c-c\ H
H
CHCH=CHp I OH
Iv
H
III
!CH&COOH
/c-c\ H
jCH,),CHO
CHCH=CHp I OH
II
~WWH
--CHz\ :
_ F-T H
H
I
R
-CH,\
-
jCH&qH 0 H
CHCH=CHp OH VI
of V
6.2. (-)-(Z}-9,17-octadecadiene-12,14-diyne-1,16-dio1
and their photopolymerizations.
[24]. They had obtained such conclusions by applications of Brewster’s rule [24]. 5.5. Kakuremino
A methanol extract of the sap was washed with hexane to remove the accompanying terpene hydrocarbons and a yellow oil remained (13.6%). TLC separation of this oil gave the results shown in Table 3. From fraction 3-3 of Table 3, (-)-(2)-9,1’7octadecadiene12,14-diyne- 1, I6-diol (IV) was obtained as a chromatographically pure sample in a yield of 2.0% after further purification by preparative liquid chromatography. The IR spectrum of IV was identical to that of an authentic sample (see Section 5.1). Fraction 3-6 gave (-)-(Z)- 16-hydroxy-9,17-octadecadiene- 12,1Cdiyne-I -yl-formate (VI).
sup acetylenes as phytoalexin
Kawazu et al. [24] also had found that IV and the free acid of V showed prefect inhibition against condium germination of Cochliobolus miyabeanus. Terada et al. found that these acetylenic compounds were much more effective to Trichophyton mentagrophytes, a fungus of water-eczema, compared with a commercial drug [25]. Therefore we suggest that these diacetylenic compounds should be phytoalexin. obtained when the tree-bark was cut.
(IV)
From fraction 3-3 of Table 3, an analytical sample (30 mg) of IV was obtained after purification using preparative liquid chromatography. The IR, UV and ‘H-NMR spectra were identical to those of (-)-(Z)-9,17-octadecadiene-12,1,4-cliyne-1,16-diol obtained already from the sap of the Kakuremino tree (Dendropanax trijdus Makino) (see Section fi.1). This sample (IV) showed [cY]~ -48.9”. 6.3. (-)-(Z)-l6-Hydroxy-9,17-octadecadiene-12,14-diyneI-yl-formate (VI) [6] From fraction 3-6 (51 mg) of Table 3, an ianalytical sample (13 mg) of VI was obtained as the main fraction from Table 3 TLC Separation of the yellow bura tree (see Section 7.1)
Table 2 Further
chromatographic
separation
of fraction
Fraction
Solvent
Yield
2-l 2-2 2-3 2-4 2-s
CHCl? 30% Et,0 in CHClj 20% MeOH in Et20 MeOH 1% HCl in MeOH
98 (20) 192 (39) 132 (27)
(mg (%))
28 (6) 41 (8)”
Form
1
Fraction
Rf
and color
3-1 3-2 3-3 3-4 3-5 3-6 3-7 3-8
co.07 0.07-0.27 0.2,7AI.45 0.455033 0.53-0.77 0.77-0.87 0.874.92 0.92-I .OO
Pale-yellow Brown oil Brown oil Brown oil Brown oil
oil
g) from resinous
sap of Koshia-
-
Yield 26 46 40 10 23 51 14 18
(mg (%)) (6.6) (1 1.7) (10.2) (2.5) (5.8) (13.0) (3s) (4.6)
491 (100)
Total “This amount
1-1 of Table
oil (0.392
means the yield of V
Total
-
228 (57.9)
A. Teruda
et al. /Progress
in Organic
Coatings
31 (1997)
81-86
85
I - Monomfw
,.,I, 200
300
250 Wavelength
I nm
Fig. 4. UV spectra of monomers Wavenumber
Fig. 2. IR spectra of monomers Takanotsume sap.
I, II (in KBr),
III, and polymers
of I and
liquid chromatographic purification. This sample showed [cx]~ -19.2”. This showed 1720 (C=O), 1180 cm-’ (HC(=zO)-OR), and lack of the -CH20H alcoholic absorption of IV at 1050 cm-’ in the IR. The ‘H NMR spectrum showed at 6 8.06 (s, lH, -CH20CHO). All other spectral data were almost the same as those for diol IV. MS: mol. wt. 302 (M+) agreed with the molecular weight of a mono-ester of IV and formic acid. Again, the methanolysis in the presence of a catalytic amount of sulfuric acid gave diol IV. Therefore, here we obtained a 13% yield of (-)-(Z)-16-hydroxy9,17-octadecadiene-12,14-diyne-1-yl-formate (VI). This gradually decomposed to give diol IV on storage. preparative
7. The characterizations [41
of conjugated
diyne polymers
In general, a conjugated diyne compound (Fig. 1, I-VI) quickly polymerizes under daylight [26] or UV-light irra-
-
II and 111.
I cm-’
Monomer
(I) (6.34 X iO-5 mol dm’3 in ethanol)
Polymer
film of I. on silica-glass
diation [27], and the polymer structure, like b in Fig. 1 for example, may be typical in the case of the co.njugated diyne [4]. Upon polymerization, the carbon-carbon double bonds in the R and R’ groups of I-VI may be co-operative during polymerization. The IR and UV absorption spectra of the dried film are shown in Figs 2-4, along with those of I, II and III. The IR-absorption bands of the monomer I at 2255 (C-C-C-C, strong), 983 and 929 (vinyl), and 692 cm-’ (C=C cis) were absent in the polymer film (Fig. 2). Moreover, new characteristic bands of the polymer of I appeared at 2195,2155, and 2120 (C-C-C=C, conjugated, all weak), and at 979 and 955 cm-’ (C=C, conjugated). Tieke et al. ascribed these phenomena to the C=C- streching modes of the polymer backbone with various C-C skeleton motions, judging from the large number of small peaks around them [28]. In addition, the structure of the polymer was supported by the finding of Baughman et al. that the polymer backbone was represented by (=C-C-C-C=),, from its Raman spectra [29]. These facts show that the polymer backbone is built up from a structure like b in Fig. 1. The UV spectrum of the polymer (Fig. 3) shows a bathochromic shift and the polymer color is, therefore, a goldenyellow. Usually, to make Langmuir-Blodgett multilayers, a
plate
0
500 Wavelength
Wavelength
Fig. 3. UV spectra of monomer
/ nm
I and its polymer.
600 I “m
Fig. 5. Fluorescence spectra of (KOSHIABURA) nm). (By courtesy of Mr Y. Matsuda.)
films (excited by UV (365
86
A. Terada
et al. /Progress
in Organic
number of conjugated diacetylenes are employed in solid state polymerization by irradiation of the UV light from a high-pressure mercury lamp; the reactions come to completion within a few minutes. These polymerizations proceed topochemically without any destruction of the layer structures, and appear as deep purple; this color changes irreversibly to red upon treatment with ethanol or chloroform. Because the net-worked insoluble polymer (b in Fig. l), which Terada et al. obtained here, is not such a high-molecular-weight polymer and does not have such a stereoregularity, it therefore shows a golden-yellow color owing to the short-distance conjugation of carbon-carbon double and triple bonds in the polymer backbone. Krieger reported that a polymer with a highly planar backbone is blue, that a slightly planar one is red, and that a highly non-planar one is yellow [30]. We also show the IR spectrum of a dried film (Fig. 2) of Takanotsume sap. This is almost the same as that of polymer I (Fig. 2). Fig. 5 shows the fluorescent spectra of the polymer films, dried film of sap of Japanese Kakuremino, and the spectrum of a Korean dish painted with Korean yellow varnish. All of them have their peaks at similar positions (ca. 530 nm). As these polymers have such a yellow appearance by the fluorescent-yellow emission, the golden color of the coating films will be emphasized greatly under sunshine UV.
Coatings
[6] A. Terada, Abstracts
Abstracts of the LVIII Biannual Meeting Japan, Tokyo, 1989, No. 1M 41.
of the Chemical
Society
of
Y. Tanoue of the LIX
and S. Shimamoto, Biannual
Meeting
Partially of the
Tokyo, 1990, No. IC6 17, p. 1167. Matsui, Sci. Anriq., 22 (1978) 48. Matsui, Sci. Antiq., 26 (1981) 15. Terada, Kagakushi Kenkyu (J. Hisi. Sci. Jpn.) Terada, Kagakushi Kenkyu (J. Hist. Sci. Jpn.) Terada, Ronshu (Discussions) of Baik6jogakuin
[71 E. PI E. 191 A. [lOI A. Cl11 A. 42. [I21 A. Terada, Ronshu 12. [I31 M. Suenaga, Nippon of Japan).
Sogen-sha Cl41 K. Yasuda, Reports
[I51 [I61 [I71 Cl81 [I91 [201 [211 [221 1231 ~241
[26] [27]
[1] A. Terada, Kagaku (Chemismq~, 45 (1990) 851. [2] A. Terada, I. Masumoto, S. Shimamoto and Y. Tanoue, Nihon Shikko (Art of Jananese Lacquer), 496 (1993) 15. [3] A. Terada, Nihon Shikko (Art of Japanese Lacquer), 428 (1988) 8. [4] A. Terada, Y. Tanoue and D. Kishimoto, Bull. Chem. Sot. Jpn.. 62 (1989) 2977. [5] A. Terada, Y. Tanoue and S. Shimamoto, Partially presented to the
81-86
presented
Chemical
to the
Society
of
lapan,
~251
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