JPS5832875A - Tannin - Google Patents

Abstract

NEW MATERIAL:A novel tannin selected from a group consisting of a compound shown by the formulaI[R<1> and R<3> are H or OH; R<2> and R<4> are H or galloyl (G for short)], its methylate, a compound shown by the formula II (n is 2 or 3), a compound shown by the formula III (R<5>, R<6>, and R<7> are H, methyl or G), a compound shown by the formula IV, a compound shown by the formula V (R<8> and R<9> are H or G), a compound shown by the formula VI (R<11>-R<14> are H or G; R<10> is H or OH), a compound shown by the formula VII (R<15> is H or COOH; R<16> is H or OH; R<17>-R<19> are H or G), a compond shown by the formula VIII (R<20> and R<21> are H or methyl), and a compound shown by the formula IX (R<22> and R<23> are H or a group shown by the formula X (R is H or methyl). EXAMPLE:3'-O-Galloylprodelphinidin B-2 shown by the formula XI. USE:An adjustor for metabolism. PROCESS:A plant such as myrica bark, chinese cinnamon, cowberry leaf, etc. is extracted with acetone, distributed with ethyl acetate and water, and subjected to column chromatography, to give tannin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to tannins useful as pharmaceuticals and methods for producing the same.

Tannins are widely distributed in the plant kingdom, and have been widely used as an astringent due to their astringent properties, and as a tanning agent to transform hides into leather. Tannin has a molecular weight of 600
~2000 has a complex structure and a single Ilf
Coupled with the difficulties in manufacturing, research was delayed.

On the other hand, useful medicinal effects based on enzyme inhibitory effects such as raging are known, and the present inventors have isolated novel tannins from many plants and have obtained medicinal effects. Check it out.

An enzyme inhibitory effect was discovered. It has been found that the compounds according to the present invention reduce the activity of enzyme proteins by binding to them.

Such compounds of the present invention are useful as metabolic regulators.

All the compounds according to the present invention are new compounds that have not been described in any literature, except for Eugeniln.

In addition, if we explain Bugenin in more detail, it will be as follows. That is, according to the present invention, from 1.6 kQ of fresh water chestnut peel (corresponding to 500 Li of dry matter)
It is possible to obtain as many as 1.79 Eugeniin pieces. In the existing method, the crude drug shoji 5
It is clear that 560 mf of Eugeniin can be obtained from 0.0g, but the present invention utilizes water chestnut peel, the waste peel from which the starch has been removed, to produce Iiin with a yield about 14 times higher. : ugeniin can be obtained.

The compounds according to the present invention include fried plum bark, cinnamon bark, beach palm, ground elm,
It can be easily obtained from plants such as rhombuses, oak bark, and lingonberry leaves by known methods such as extraction with acetone, ethyl acetate:water partitioning, and column chromatography.

The extraction method according to the present invention can be summarized as follows, and will be described in detail below with reference to Examples.

Example 1 Extract Yang Mei Peel 60# with 5J of 8θ% aqueous acetone, distill off the acetone, divide the aqueous solution about 10 times with ethyl acetate 11, collect the ethyl acetate soluble part, and extract 5ephadexL.
Solvent ethanol with H-20.

Separation and purification by column chromatography using 80% aqueous methanol gave 70 cm of light brown amorphous powder. [α)
+73.2° (C=0.93.MeOH)"H-
NMR (acetone-d, -1-C11,0D) δ
: 3.02 (2H, m, 4'-2H), 4.01
(IH, br, 8.3-H).

4.84 (IH, br, 8.4-H), 5.1
4 (2H, hr, S, 2.2hi 11).

5.62 (IH, br, S, 3'-H), 5.9
2 (IH, S, 6'-II).

5.99(2)(,8,6,8-H), 6.48(2
H, S, 12.16-H).

6.66 (2H, S, 12', lfi'-H),
7.04 (2H, S, gal, H).

"C-NMR (acetone-ti, 4-CD5O
T) ) δ: 36.5 (C-4'l.

-g: 10.10'), 106.2.106.5.
(C-12,16,12: 16'), 110.1(
2Xgal, C-2), 121.3 (g&Ik, C-1
), 130.2, 131.3 (C-14°14+),
132.8 (C-11,11'), 138.9 (ga
l, C-: 4), 145.5 (2Xgal,
C-3), 146.0 (C-13,15,13,15
), 154.2.155.3゜155.7.157.
2.157.7 (C-5,7,9,5: q: 9')
, 166.0 (-Coo) This substance has been determined to have the following chemical structure: n, 3'-0-Oalloy
It was determined to be lprodelphinidin'B-2.

lT Similarly, 3.3'-Di -0-galloy
lprodelphlinidin (yield 002%) (
A pale brown amorphous powder lamp was obtained.

[α)”-60,9°(C-0,87, acetone
)*”H-NMR(icetone-(1,)δ:
2. '18 (2TL m, 4'-H), 4-78
(IH, d, J=3I-1z, 4-H), 4.9
6 (IIL m, 3'-H), 5.40-5.5
6(2it Tn, 3-)I, '2'-H”), !
1.56 (IH8, 2-I-I), 5.96 (21-
L m, 6.8-11), 6.11 (IH, 8,6
'-H), 6.50 (2H,S, 12.16-II)
, 6.53rzx(,8,12,'16'-H),
6.96 (2H, 8, gal, H), 7.07 (2
1(S, gal, H) 1(LJ Similarly, 3.3'-Di -0-Galloyl
prodelphinidin B-9 (yield 0.04%
) (pale amorphous powder) was obtained.

[α)--022° (C=1.29-MeOH), C
MR (CI) aOD ) δ: 27.3 (t.

C-4'), 36.1 (C-41,69,2(C-
3'), 76.8 (C-3'), 79.0 (c-
21).

81.7 (C-2), 96.1 (C-6), 9
7.4 (C-8), (18,5 (C-6), 99
．． 8゜106.4.107.1 (C-8,10,to'
), to7. o (c-tz, 16.12: 16ゝ)
.

110.3 (gal, C-2), 120.7.12
1.1 (gal, C-1), 130.1.130.
7 (C-14,1a), 134.0.134.2 (C-
11,ll'), 140.0,140.6(gal,
C-4'), 145.7.146.0 (g&II,
C-3,5), 154j5.155.0°155.6
．． 156.5.1570.15B, 1(C-5,7,9
, 5: 7: 9'), 167.1°168.3(-
〇〇〇-) Note* 3.3'-DI-0-G&+1Ioylpr
When odelphinidin B-9 is hydrolyzed with tannase, the following substance is obtained (colorless needle crystals). m
, p.

234υ(dec,) [α)”;+95.3°(C: 0.575.Me
an ) PMR (DM80-ds') ppm:
2.73 (2H, m, 4'-T(), 3.98(
IH, br, S.

3-11), 4.12 (ll-1, br, S, Go H), 4.23 (IH, 8, 2'-H), 4.32 (1
)(,S, 4-H), 4.70(II(,8,2-
H), 5.65.5.73 (each 1) f.

d, J=2Hz, 6.8-I4), 5.89(1
)(,S, 6'-H), 6.34.6.48(ea
ch Example 2 The following substance 2Q119 was obtained from 9.7 kq of cinnamon using the same method as in Example 1. Yellowish-brown amorphous powder.

[α); +'15.7° (Cm0.465. acet
ne)PMR(acetone-da)pprn
:2.87 (2It rll, Cj'-H), 4.
12 (3I upper hr.

8, Cs+s;*'+ -H), 4.38 (I
H, br; 8. C, H''-H), 4.81-4.
88 (3TI, m.

Cm, a', a''-H), 5,055.27 (4I(
, m, C, product 1t-H), 6.00.6.04 (5
11in total, S, C,, i, t, i:s
-fT), 6.84-7.16 (12TL +n,
Ar-11) CMR (acetoneAr-11)C
:282 (CI”), 36.8 (C4, a', /), 6
6.0 (Cs-).

72.0. 72.3 (Cs-m-*”), 76
．． 6 (CIl, l-m...), 7s 9<C,-
;r, 95.8. (16,0°(C1□1..
1.・；、!・U, 144.7, 145.0 (C1s,
sa, xm:la; xs':1j:Ij':xi'),
1.53.7°1542.155.6. 156.0.
156.5, 157.1, 157.8 (CIl, y, s
,s・,y;ij'ite r4ase+1'Cinnamtannin l Example 3 The following substance 240■ was obtained from bottle wax 1.2# in a manner similar to that of Example 1. Yellowish-brown amorphous powder.

[α) , +98.6° (Acetone, Cm1
．． OO) PMR(Acetone-d, +I%0
1 ppm: 2.60-2.80 (2) L rr
lICa-Hl).

4.04428C4um, Cbdm';d"H)
, 4.72-4.88 (3) L m-Ca, a', a''
-H), 4.97 (1) L d, J=8.0Hz
, Cd”-H), 5.12(11-L b r,s
, C, -H), 5.20 (I11μ br; s
, to □-H), 5.31 (IH, br; s,
C/4-H), 5.96-6.20 (5T(i
n total, m, 6. 6', 6'
, '6': 8-H), 6.64-728 (12
niAr-H) CMR (Acetone-da +DmO'j pp
m: 36.8 (C414; 4″), 67.4
(C5-).

? 1.4. 71.8. 72.8 (CI, 1tfi=
), 76.5 (C1,l-/l), 81.3
(C1='), 95.6°96.1.96.9(C
'a, s, s; s;'s'')m 100.4.100.
9.101.4 (Cue1ma notification ++l”).

106J, 107.3 (CI-sl'*"'),
114. o, 114.8. 115.5 (C
xs, +i, us;xi;□・;1 ink';11shi111
1・”), 118.6(Cxs, utxs?x・f
”)-131,8(Cm-mj,f;tx-), 1
44.5°144.9. 145.1 (Cxs, xa,
xj, maStj; mj';tj','n''), 1
53.2. 154.0. 154.8°155.8.
15 ξj9. 156.4. 157.8. 15
7.6(Cs, y, s, r; y; s', j, y7.g"
, y:'s") IJ Arecatannin A-1 Arecatannin was obtained in the same manner. Yield 0
．． 01% yellowish brown amorphous powder.

[α), +117.2° (Acetone, Cx1.
9) PMR (Acetone-da +D*O)
ppm: 2.60-2.80 (2H, m, c/
'-) Yes.

4.04-4.28 (5) L m + Cm, j
*I'+l? l"H) # 4.76-4.92
(41L mm C4+ a-a, m-H),
4.95 (IH, d, J=8.OHz, Cj”-
H), 5.12 (IH, b(S, c.

-J(), 5.20 5.40r3) -T, m
, Ct-/lr H), 5.96-6.20
(6H1ntotal, l'n, 8. f),
616; 6'l'6"H) h e, e +-72s
(i 5H, ml A-r-■() CMR (Ace tone d@ 10 DaO) pp
m: 36.9 CC414t4':X, 67
．． 5 (Cs”u.

76.5 (C1+, -j;z”'5, 84.4 (C
j' U, 95.7. 96.3. 97.1 (Cs
, wts';a';'a...).

100・4・101.3 (C1o-to'-1ir
+ Easy [1・”A, 1.06.5. 106.9.
107.2(C4',j;ffi2,-x114.4
．． 114.5. 115.4 (Cu, xg, um
j, n';fj:x;t+jc1;xi''), 11
8.5 (Cxa.

3. -, Mu product'='), 131.7 (C□I+11+1
-', bar, 1, 144.5.144.9 (Cus
, ta, u', xa'.

s: glance s4', 'sr, s;:'sJ'?), 15
3.1. 154.0. 154.8. 155.3.
155.9. 156.2°156.3,157.0
, 157.6 (Cs, t, s, stt-m', sτ-;
l+M+4: @N71N” Arecatanni
A-2 In the same manner, Arec&Itannin B-1 (yield 0.01%) (one-yellow color amorphous chrysanthemum chrysanthemum was obtained.

[C3,1ate°(Acetone, Cm1.OO
3PMR (Acetone-da +DsO) ppm
: 2.60-3.0 (2)1. m, 4″′-1
1,).

3.90-4.30 (4H, m, Cm, *'+L?'
-H'), 4.55 (111, d, J=10Hz,
C, '+'-H), 4.76 (IE br, s,
C,'-H), 4.82(III, br; s,
C4-H), 4.90 (IRJs, C4”
-'H), 5.08-5.36 (3H, nl,
C,,i,! '-H), 5.96-624C
5Hin total, m, 6, 8. 6. '6
:'3'''I('), 6.64-728C121
Cm, Ar-H) CMR (Ace zone-da +DtO) ppm
: 37.1 (Ca, *'**"1. 68.0
(C4”r.

? 1.0. 72.0 = 72.7 (Cm, st
s'U, 76.5(C-', /:rU, 82.1(
C-U, 95.6. 996.0. 97.0(C
s-*, js? j, 100.0(Ct=”)I
101.0. 101.2 (Cn, xs', m=').

ioe, s, 107.1. 107.3 (C to st
/), 114.6. 115.1. 115.5 (
C11, ms.

xl-xi; t4 zz; 1jZ♂), 11B
,4. 119.8 (Q@, ts-zj-t/U,
131.3. 131.5°131.7 (Cxi+xt
',z(;z(''), 144.4. 144.6.
144. (1,145,0,145,5(C,l.

x41xm', zjuhdm&im-, 154,0,1
54, 3, 154, 9, 155, 9, 156, 5, 15
7,0°157.6 (Cg+v++++gSy;j+
j+j*es4y;s'')11() Arecatannin B-1 Similarly, Arecatannin B-2 (yield 0.004%) (one-yellow colored amorphous powder) was obtained.

(α), +86.3° (Acetone, CzO, C
4) PMR (Ace tone-da-IJ), o
) ppm: 2.60-3.0 (2H, m,
Ci”-HI).

4.52 (11-T, d, J-10Hz, C,
"U I 4.64 (21-II br, st
C414'-H)14.76 (2T1.l)(
s, Cl: /'-H)+5.00-5.40
(4K ml C**i*i-1'-H)+5.9
0-6.20 (6H, in total, m, 6.
8.6.6.6g'8-)1"l, 6.50-7.2
0 (15I(m, A r-H)Example 4 The following substance 300cm was obtained from 3.O# in the same manner as in Example 1. Yellowish brown amorphous powder.

[α)' Knee t7o, t° (Cm0.72. Acet
one ) PMR (DMSO-da, 150°) pp
m: 2.36 (III, dd, J=16TIZ,
BH4C,'-H), 2.70(11(, dd, J
=1611r, 5Hz, Cm'-If), 35B
(III, m.

C1″-H), 4.43(IT(,d, Js-
4=8fh, C,・-11), 4.56(11
1, (+, Js,,=8Hr, C,-IT),
4.65(llt d, J,,,=7H2,C,-H
), 5.71 (IH.

d, Js, 5==2Hz, c, H), 5.77C
1) (d, Js, @'=2Hz, c, H).

5.88(114,s, Cs'H)-5,92(N
-1t, J=7H2, Cs H), 6.30-6.7
3 (61L IL Cs**, s+xa*x7x
st, s' I(), 6.72 (2H, s,
gal Ioyl-H) CM1? (Acetone
-da) ppm: 27.5 (t, Ca'),
36.0 (d, Ca), 6g, 1 (da C
s'), 72.9(tL Cs), 81.0.81
．． 9 (each d, C,, C,'), 96,5°97.2 (eacl+ d, Cm, 1)*
100.4 (S, cll), 101.5
(So ca ) + 105.2 (s, Q*'
)-109,7(d, gal Q, a), 114.
9.115.3.115.5.116.9(”Cs4
Cxx41+111+IM')l 119.2#
120.3 (each d, C1@, 16, 1
21.6 (1, gdl-c) + 130.5.131.
3(each s, Co, CH') + 138.0(
s, gal'4) I 144fL 144.8
(each s, Q1114111;Ij)1
145.3 (S, gal-C.

g), 154.4.154.6.155.0.155
．． 3.155.5.156.7.156.9.157.
6(eachS*Cs+y+e+ity+s')+16
5.0($+C=O)3-0- galloylpro
cyanldin B-3 Me, So4.
By adding K, Co, and refluxing in acetone for 3 hours, methylage of this product was obtained with a yield of about 60%.
Ru.

Amorphous powder. [α)D-170,0°(Me, CO, C
m0.72) Example 5 The following substance 1.82 was obtained from rhombus 1.6 klj in the same manner as in Example 1. Yellow needles.

m, I), 248-250℃ (decr+ml)+
[α]”: +106.2° (Cm0.83°1c
etone) AnalCalcdforC411%@O1y・2)%
0IC149,71:1(3,46Found:C,4
9,46:H,3,78"H-NMR (Acetone
-d,)δ: 7.16.7.12°7.06(eac
h2)Ls, galloyl IT), 6.3
6 (IIL d, J=811z, C, -H).

6.02 (IIL t, J=10Hz, clH)
, 5.80 (II(-t, , T=10I-1z,
c, -H), 5.76 (II-L t, J=10H
z, C, -H), 5.16(1)1. d+l,
J=6.1011z.

Cs Hr), 4.18 (ITi, d, J=l
OHy, Cm-Ha), 4.40 (IH, 5ex
tel.

J=6.10Hz, Cm H), 4.66(IH,s
,Q''H), 6.82(11(,s, CI'-H)
, 6.40 (11-T, s, Cj'-H), ”
C-NMR (Acetone-d,) δ: 168.2° 166.3.166.0.164° 8.164.1 (-
COO-), 119.6.119.4.118.9(
galloyl C-1), 109.9(galloyl
yl C-2, C-6), 145.7 (galloy
lC-3, C-5), 139.7.139.3 (ga
lloyl C-4), 112.3 (C-1').

122.8 (C-2'), 107.6 (C-3'),
141.9 (C-4χ135.5 (C-5').

150.8 <C-6'), 42.7 (c-1'
'), 119.4 (C-2''), ta 1.0
(c-i').

191.8 (C-4"), 96.4 (C-5°'
), 91.1 (C-6'), c+2. acc-t)
, 70.9 (C-2), 72.7 (C-3), 68.
9 (C-4), 73.2 (C-5), 65.7 (C-6
) Trapain Example 6 The following substance 30011% F was obtained from Yang Mei Peel 6.0# in a similar manner to Example 1. Pale brown amorphous powder.

[C1: +57.4° (C-1,0, acetone)
, 'H-NMR (acetone-da) δ: 3.
05 (2H, m, 4'-2N), 4.63 (IH,
S, 4-H), 4.90 (IH, S, 3-H), 5
．． 05, (IH,S,2'-H), 5.50(I
H, S, 3'-) 1), 5.61 (IH, S, 2-H)
.

6.41.6.08.6.19 (each IH,S,
6,8.8'-H), 6.54.6.70(eae
h 2H+ So 12. N6,12: 16'H)
+y, oa, 7.12 (each 2H+8,
gal, H).

3.3'-DI-0-Galloy prodel
Similarly to phinldin B-5, 3.3'
-Di-Galloyl prodelphInldl
n B-10 (yield 0.002%) (pale brown amorphous powder) was obtained.

[α]: + 17.4° (Cm1.16. acet
one) + 'H-NMR (acetone-da) δ
: 3.00(21(,S, 4'-2H), 4.6
6 (IH, S, 4-H), 5.05 (IH, S,
2'-H), 5.15 (IH, S, 3-H),
5.33 (IH, 8, 2-H), 5.58 (IH, S
, 3'-H), 6.00 (IH, d, J=2Hz
, 6-H).

6.12 (IH, d, J=2Hz, 8-H), 6
．． 16 (IH, 8, 8'-H), 6.53°6.64
(each 2H,S, 12.16.12: 16'
), 7.04 (4H, S, gal, H).

Example 7 The following Ga1loyl glucose 30'jv was obtained from Rhombin seeds 1.6 & 9 in the same manner as in Example 1.

S color amorphous powder ['']: + 48.58 (C: 1
．． 00. Me*CO), 'HNMR (acetone-d
s) δ: 6.98-7.20 (6H, galloyl
-H), , 6.12 (IH, d, J=8Hz,
C, -H), 5.62 (IH, t, J=8Hz,
Cs-H).

5.42 (IH, t, J=8H1, Ca-H), 4
．． 02 (IH, br, t, J=8Hz.

76.1 (tL C,), 71.6 (d, CI
), 69.1 (d, C4), '61.7 (t
, cs).

1,2.3-Tri-0-galloy1glue
Methyl-2 was obtained from the ose District Public Prosecutors Office in a similar manner.
,3,6-Tri-0-galloyl glucos
e (colorless amorphous powder) is obtained. Yield 0.00196 [
α) enemy +84.3° (Cm1.Oacetone) PM
R (acetone d@), ppm: 3.44
(3H+S, -○CIm), 3.90~3
．． 96 (2H, m, C4-H, Cm-H), 4.5
6 (2H, m, Cs-2H), 4.76 (IH, d
, J”8Hz, Ca-H), 5.16(IH, d
, d, Ct-Hl, 5.50 (IH, m, C
m H), 7.02.7.19 (6H, each S
, galloyl-H).

CMR (acetone ds) ppm: 56.8
(an 0CHI), 64.0 (L C1) 169.
6 (d, α), 72.5 (d, Ct), 74.8
(d, CI), 76.1 (d, cl).

102.2 (d, Ca), 109.7 (d, -g
alloy-Ct, 6), 120.4.120.
5゜120.9 (each, 8. galloyl-
Ca), 138.8 (S, galloyl-C,)
.

145.7.145.5 (each S, gallo
yl-Cm, 11.165.8.166.6°166
．． 9 (sach S, -Coo-).

Similarly 2.3.4.6-Tetra-0-ga from Jiyu
lloyl glucose (yield o, o i 96
). Yellowish-brown amorphous powder.

PMR (acetone ds), ppm: 4.1
4-4.70 (3H, m, Cs-H, Ca-H)+
(8H, m, galloyl-H).

Lee Example 8 Almost the same method as Example 1 from 6.3 # of Japanese oak bark
From this, 45 da of the following substance was obtained.

Colorless amorphous powder. [α) D-102,8° (C=0.
32. ace tone )PMR(acetone
-da) ppm: 2.10-2.50 C4H+
m+ Ct, 6-H)+4.50(IH, d-1i
ke, J=4Hz, C--H), 5.25 (IH
, dd, J=7°411x, C4-H), 5.6
0-5.93 (IH, m, C5-H), 7.05.
7.11 (each 2H+ Sr gal, H).

CMR (acetone-do) ppm + 38
．． 0 (Cm), 39.0 (Ca), 68.5 (CI
).

68.7 (C-), 715.2 (C,), 75.5
J(C4), 109.7.109.8(gal, C
m, s).

120.6 (gal, CaX 2), 138.7
(gal, C4X 2), 145.5 (gal
, Cs, t X2).

166.3, 166.6 (-Coo-), 177.5 (
-COOH).

G3,4-Di-0-galloyl quinic
acid.

Similarly, 3.5-Di-07gaJloyl qui
nic Ac1d Colorless amorphous powder (yield o, o o
e%) was obtained.

[“), -63,0” (°=0.20・“°°′°”
°),.

PMR (acetone-do) ppm: 2.3
3 (4H, d-1ike, a=7)&, Cm,
6-H), 4.14(IH, d(L J='1.4H
z, Q H), 5,40 5.68 (2H, m,
Cs, --H), ? , 13.7.19 (each
2H, 8, gal, H).

CMR (acstone d@) ppm: 35.7 (
CI), 37.5 (CI), 70.1 (α).

72.0 (Cm), 72.1 (Cs), 74.2 (
CI), 109.8 (gal, c recommendation 5X2), 12
1.4°121.9 (gal, Ca), 138.
3.138.6 (gal, CI), 145.5
(gal, Chm X 2) 1166.1 (-Coo
-X2), 175.8 (-COOI().

H Example 9 Extract 6.3# of Japanese oak bark with aqueous Ashiton 51,
Separate the liquid with ethyl acetate 11, collect the ethyl acetate soluble part,
Purification by repeated column chromatography separation using 5ephadex LH-20.

The following Ga1loyl 5 alidrosides were obtained.

1. Yellowish brown amorphous powder (yield 0001%) [α]n
+ 4.5 (C=0.51MeOH)PMR(CO
mOD) ppm: 2.83 (2H, t, J=
7Hz, -CHx-φ).

3.3-4.2 (glu, CI+4,1.@-H)
, 4.42 (IH, d, J=8Hz, anomH
), 5.12 (IH, t, J=10Hz), 6.
68 (2H, d, J=8Hz, Cs, g”H).

7.50 (2H, d, J=8Hy,, Cm, *
-H), 7.12 (2a S, gal, H).

CMR (CD, 00) ppm: 76.2 (t
, -CHt-φ), 12.3(t, glu, Cs
).

69.7 (d, glu, C4), 72.1 (t,
-CH3-φ), 73.4 (d, Hlu, Ct).

77.6 (d, glu, Cs), 79.0 (
d, glu, Cg), 104.0 (d, Q),
110.2 (gal, Cats) + 115.9 (
tL Cabs) 1121.5 (s+ gal-CI)
+ 130.5 (!l.

CI) + 130.7 (BI C Kan +,) 1 13
9.4 (8+ gal -α), 146.0 (
s, gap.

C heat, s), 153.6 (II, C4), 167
．． 9 (8Coo).

2. Pale yellow needle crystals (yield 0.5%) mp, 116-117υ [α), + 15.1° (Cm0.9. aceto
ne) PMR (acetone-da) ppm:
27.8 (2H, t, J=7Hz, -CHt-φ
)13.30-4.10 (glu, Ct, s+i+
*-H)+4.40 (IH, d, J==8Hz
, anom.

H) 4.41 (IH, d, d, J=12.4Hz,
glu, Cm-II), 4.58 (IH, d, d
.

J=12.2Hz, glu, Cm H)+6.7
2(2I(,4J==8)1z, Cabs H)+
7.03 (2H, d, J=8Hz, CI, @
H), 7.17 (2H1S1ga1.H).

CMR(acetone-dJppm:35.7(t+
CHg-φ), 64.4(t, glu.

CI), 71.0 (t, OCH*), 71.4
(d, glu, C1), 109.6 (d, gal
, Cars)+115.6 (d, Cm, w), 1
21. OCa, gal, CI), 129.7 (
s, CJ, 130.3 (d.

Q,,), 145.6 axis + gal-CI+6)+
155.9 (s, α), 166.9 (s, -CO
O).

3. Colorless amorphous powder (yield 0.00296) [α),
+20.9°(C==0.3.acetone)P
MR (acetone-do) ppm: 2.80
(2H, t+ J=7Hz, -CHt-φ).

3.32 4.04 (glu, (J+411 H)
, 4.20 (IH, dd, J”12.4Hz.

glu, Cs-H), 4.42 (IH, dd,
J=12.3Hz, glu, Co-H).

(each 2H, m, gal, H).

CMR (icetone-da) ppm: 35
．． 7 (-C)hφ), 63.5 (glu, C6
).

71.5 (glu, C4), 72.0 (OC&),
72.5 (glu, Ct), 74.5 (glu,
ct).

75.2 (glu, Ct), 103.6 (glu,
CI), 109.7.109.9 (gal, ct,
s).

115.7 (CI, v), 120.5.120.8 (
gjLl, ct), 126.9 (CI), 130.
4 (Cm, J, 145.7 (gap, Cm, m
X 2), 155.9 (α), 166.5. 1
66.8 (-COO-).

4. Colorless amorphous powder (yield 0.OO2%) [α) D-2
1,0°(C:=0.31.icetono)PMR
(acetone-dJppm: 2.91 (2H, t,
J=7Hz, CH! φ).

3.10 4.12 (glu, Cbm, 6m H)
, 4.36(1)L dd, J”12°6Hz+
glu, CI-H) + 4.40 (IIL do
J=8Hz, anom, H)+4.58(IH, d
d, J=12.2Hz, glu, CI-H),
7.07 (2H, d.

J"8H2, Cal H), 7.19 (2H, d,
J=8H,Ct,sH), 7.197.26(
each, 2L Ill gal, H).

CMR (icetono-ds) ppm: 36.0
(-C)hφ), 64.5 (glu, CI).

71.0 (gin, C1, -OCH*), 7
4.2 (glu, Ct), 74.5 (glu,
Cs).

77.2 (glu, Cs), 103.6 (glu,
CI), 109.6.110.01gm1-C*+
・)+120.3.121.0(gal, C,),
1211(C,,,), 130.4(Q,@), 1
36.8 (CI), 13B, 7.139.3 (gal
, CI), 145.7.145.8 (gal, C
m, g).

150.1(C,), 165.7.1.67.0(-
COO-).

5. Pale yellow amorphous powder (yield 0.004%) [α) D-3
6,2° (C==0.24. acetone) PMR
(acetone-d,) ppm: 2.75 (
2) Lt, J=8Hz, -Cbm).

3.2 4.08 (glu, Ct+s+4+s H
) + 4.39 + 4.58 (each IHldd.

J=12.12Hz, glu, C5-H), 4.
40 (IH, d, J=8Hz, anom.

H), 6.53 (IH, dd, J”8.2Hz,
Cm H), 6.71 (IH, d, J=8Hz,
C6I(), 6.74(IH,d, J=2Hz,
Ct-H), 7.17 (2H,s.

gal, H).

R'R" R Hatake R' R Mo I
HHHGH 2Ml (HHG 3 HHGHG 4HGH) IQ 5 0HHHHG Example 10 From the bark of Japanese oak, in the same manner as in Example 9,
The following galloyl quercitols were obtained.

1. Colorless amorphous powder (yield 0.7%) [α]D-107.2° (Cm0.67, MeOH)
PMR (acetone-ds+cDaOD) ppm:
2.04 2.20 (2H, m, Co-H), 3
．． 29 4.16 (3H, m, C+1tll H)
, 5.38 (IH, dd, J=:lQ.

6Hz, C=-H), 5.60(IH,t, J=
10Hz, α-H), 6.98.7.04 (eacl
t2) I, s, gal, H).

CMR (acetone-da + CD5OD)
ppm: 32.7 (LCm), 69.4
(da c+).

70.7 (d, CI), 71.4 (d, Cm
), 73.9 (d, CI), 75.6 (d,
C,), 109.7°109.8(d, gal,
Ct, s3.121.1.121.3(s, gal
, Ca), 138.6 (s.

gal, CaX2), 145.8(a, gal,
cs, gX2), 166.6.167.4 (s.

-COO-) -G 4.5-DI -0-galloyl quereit
o12, colorless needle crystals (yield 0.006%) mp255-258°C [α]D-10,5° (Cm0.68. aceton
e) PMR (acetone-ds) ppm:
2.10-2.30 (21-1, m, C5-H),
4.18゜4.29 (each IH, a-1...(
eI C8+t H) 15.40 5.76 (2H
, n, Cs, sH), 5.90 (IH, t, J=
10Hz, C4H),? , 00.7.05.7.08
(each 2H+ s, gaL H).

CMR (acetone-dJ ppm: 32.
3 (t, CJ, 69.3 (d, Ca), 7
1.2 (d.

Cy, s), 72.4 (d, α), 73.2 (d,
Cm), 109.7(d, gal, Ct+5X3
)+120.5 (s, gal, Q X3 ),
138.9 (s, gal, CaX3), 14
5.5 (m.

gal, cs, vX3), 166.5(s, -CO
O-X2), 167.1(s, -Coo-).

H G 3.4.5-Trl-0-galloyl quer
citol Example 11 The following substance was obtained from elm in the same manner as in Example 9.

Yellow-brown crystals. mp, 209~'2107) (Yield o, o0296) [α), +38.8° ()hOace
tone, 8:2. Cm0.79) AnaL Ca
1cd, for (wHs+o+s ・HtOC, 4
9,56: I■, 4.00Found C,4
9,47: H,4,05PMR (acetone-d
a) ppm: 5.30 (d, J=8Hz, α
-CsHorβ-Cm-H), 5.50.5.1
52 (each s, α-C, -H, β-Ct-H),
5.64 (d, J=8Hz, α-Cm Hor
β-Cm H), 7.04 7.40 (6H, m.

galloyl, H).

CMR (CDgOD) ppm: 65.0 ((ff
i-C,), 66.8(β-C,), 67.0(I
X-CI), 67.2 (β-CI), 73.6 ((
ffi-CI), 75.6 (β-Cs), 78.9
(α-Cm), 79.3 (β-Cs), at, s(
a, β-04), 98.4 ((L Ca), 10
3.1 (/Ca), 110.1 (galloyl
Ct, Ca), 120.2.120.5.120.
7゜121.0 (galloyl-Ca), 1
39.7 (galloyl-Co), 146.1
(galloyl -(J, Cs), 167.5,1
67.7, 167.9, 168.1 (COO).

3-0-Galloyl hamamelitannl
If this product and MeSO4, KJcOs are refluxed in acetone for 3 hours, a methylate (colorless amorphous powder) of this product can be obtained with a yield of 60 to 70%.

[α): +22.5 (Cm0.32. CHCl,
) Example 12 Cowberry leaves 1.8# were digested with 37 g of acetone, and after distilling off the acetone, it was dissolved in water and partitioned several times with ethyl acetate (11). The acetic acid transition part was subjected to 5ephadex LH-20 column chromatography, separated repeatedly, and then Me=S
The following substance was obtained by methylation using α and KtCO in a conventional manner.

1. Colorless amorphous powder, [α]. +72.7゜Proto
n-NMR [PhNα-ds, 150υ] 2.65 (
IH, dd, J=8.16Hz, α”-H) 3.18(
IH, dd, J=6.16Hz, CI-H) 3.5
4-3.96 (OMeXll) 4.48 (IH, J=8 out, Cj'-H) 4.60
(IH, m, Cs' H)4.92 (IH, d,
J"2Hz, C4H) 5.03 (IH, J=2) (z,
Cj-H)5.90(IH,)r,s,C
Meng-H) 6.14 (IHld, J=12Hz, Cm
H) 6.29 and 6.44 (each IH+ I
h C6Cj'-H) 6.38 (IH, d, J
"2Hz, Cm H)2, colorless amorphous powder, [α)
, +107.9° Pro ton NMR (PhN0
m ds , 150υ] 2.68 (IH, dd,
J=8.16Hz, CJ'-H)3°18(IH,d
d, J=6,16Hz, c;・H) 3.24~3-
99 (OMe X 11.:) = 74.46 (IH
,d, J”8Hz, Ct”H)6.08 (IH
, d, J''2Hz, Cs H) 6.24 and 6.45 (each IH, 8, Ca, Ca-H) 6.
35 (IH, d, J=2Hz, Cm H) Example 13 1.6 kg of rhombus peel was mixed with 3.5 kg of acetone. / to remove acetone and partition the aqueous solution with ethyl acetate (11).

The acetic acid transfer part was applied to a 5 ephadax LH-20 column chromatograph, and Eugenil having the following structural formula was added.
n 7.79 were isolated.

Above Patent Application No. 120372 filed in 1982 2. Name of the invention Tannin 3. Relationship with the case of the person making the amendment Patent Applicant Address 14, Kisshoin Nishinoshomon Rocho, Minami-ku, Kyoto 601
Address name (415) Nippon Shinyaku Co., Ltd. President Hiroshi Morishita 4, agent residence 14, Kisshoin Nishinoshimon Rocho, Minami-ku, Kyoto 601
r on the 4th line in parentheses below the number 3-0- Ga1loy
l e-*J, correct r-0-J to r-0-J.

(2) On page 8, line 7 of the specification, [C=0.934 is corrected to [a=0.93J].

(3) From page 8, line 8 to line 12 of the specification, 9t
Correct "S," in all M places to "S,".

(4) On page 9, line 2 of the specification, [0-Ga1loyl...
...", correct "〇-" to "0-".

(5) j 3.3'-DI on line 8 from the bottom of No. 9 of the specification
-0-galloyl"・" is replaced with [3,3'-
Corrected to "Di-0-Galloyl"・J.

(6) l”Cm0.87J on the 6th line from the bottom of No. 9 of the specification
Correct the statement to [c=0.87J.

(7) In the fifth line from the bottom of page 9 of the specification, the text "r4-78J" is corrected to "4.78 J.

(8) From the 3rd line directly below No. 9 of the specification to the bottom line,
Correct all six occurrences of "S," to "a,".

(9) rc='1.29 on page 10 of the specification, line 9 from the bottom
J is corrected to [a=1.29J.

r(C: 0.fi75.
MeOH month is r (e = 0.575. Me
OH) Correct to J.

("S," in seven places from page 11, line 6 to line 10 of the Ill specification is corrected to "S," in all cases.

The chemical structure is corrected to the chemical structure listed on the bottom line of page 41 of the O2 specification.

αJ specification, page 12, line 4: j(C==0.465.
a::etne)J is replaced by r(e=0.465.
acetone) Correct to J.

The three places from line 6 to line 8 of page 12 of the Alphabill Specification that say "S," are all corrected to "8."

■Correct the statement rc=1.00J on the 8th line from the bottom of page 13 of the specification to [c=1.00J.

(To) rArecata on page 14 of the specification, line 5 from the bottom
Insert rA-2J after nnin J.

, rc=1.9J in the third line from the bottom of page 14 of the αη specification is corrected to [C=1.9J.

In the 4th line of page 16 of Ql Ming Pongshu, [c = 1.00J is corrected to ``c = 1.00J.

r95.6 on page 16, line 12 of the alpha specification. Delete the "9" after the J.

On the 6th line from the bottom of page 47 of the Kan Specification, rc=o, 04J is corrected to [c=o, 04J.

Co., Ltd., page 48, line 4 from the bottom of the specification [c=o, 72J
``Corrected to C20,72J.

Co., Ltd. At the bottom line of page 19 of the specification, r3-0-gallo
yl”-J is r3 0 Ga1loyl
5ees J, corrected.

rMs*cO, C=0.72 on page 20, line 3 of Nichimei Tsumugisho
J is rAeetono, e:=0.72
Correct to J.

In the 7th line of page 20 of the specification, rc=0.83J is corrected to rc=0.83J.

(To) rcs-Hl on page 20, line 14 of the specification), 4
．． 18 (IH, d, J=10Hz.

C, -11,)J is rC, -HA),, 4
．． 18 (IH, d, J=10Hz, C.

-HB) Correct to J.

(To) Change the "C-" in the third line of page 22 of the specification to "
Correct to "C;".

On page 22 of the Section Specification, lines 5 to 9, all eight places where the word "S," is written are corrected to "S,".

(Support) In the second line from the bottom of page 22 of the specification, [3, t-DI-
What is Gallo-kari is “3.3'-Di-0-Ga”.
Corrected by lloyl J.

The nine places that say "S," from line 2 to line 6 on page 23 of the Kan Specification are all corrected to "81."

(1) rC on page 23, line 10 of the specification: 1.00.
Me*COJ means [c = l, QQ, Aee
Correct to tone J.

Group) All four places that say "S," from the fourth line from the bottom to the second line from the bottom of item 23 are replaced with "S."
,” is corrected.

(To) rc=1 on page 24, line 5 of the specification. OJ means jc=1. Correction to O.J.

On page 24 of the Zeng Specification, from line 6 to line 15, all six places where it says "S," are corrected to "S,".

rc=o, a2 on page 25 of the specification, line 8 from the bottom.
Correct the statement to [e=o, 32J.

(To) Correct "S," in the fourth line from the bottom of page 25 of the specification to rs, J.

(To) On page 26, line 6 of the specification, rc=0.20J is corrected to ``e==o, 20J.

1. On page 26, line 9 of the specification, "S," should be replaced with "I,"
Correct.

(To) "C20,5" on page 27, line 7 of the specification is corrected to [c=O,RJ.

(To) On page 27, line 8 of the specification, there is “cO, ODJ,”
On the 12th line of the same page, [cD, OOJ] are both corrected to "cD, ODJ.

(g) Insert "rs glu, Cs H" after "rJ=toHz" on page 27, line 10 of the specification.

(In Sen Specification, page 28, line 3, rc=0.9J and 17
) is corrected to rc=o,9.

(Transformation) On page 28, line 8 of the specification, "S," is replaced with "8.
．． ” is corrected.

(c) Correct "rc=0.3J" to "re=0.3" on page 28, line 14 of the specification.

(On page 29, line 8 of the 441 specification, [c=0.31J is corrected to [c=0.3 month].

(45) In the second line of page 30 of the specification, rc=o, 24J is corrected to ``a=0.24J.

(The statement ``C=0.67J'' on page 31, line 5 of Samei Tsumugi is corrected to rc=0.67J.

0η On page 32, line 3 of the specification, [c=0.68J is corrected to [e=o, 68J.

(The second line from the bottom of page 32 of the Gyomei Tsumugi Book says rc=0.79J, which is corrected to [e=0.79J.

(The statement "c=o, s2" on the bottom line of page 33 of the 4-wound specification is corrected to je=0.32J.

Written amendment to the above procedure (voluntary) Patent Application No. 120.372 of 1981, 21 Name of Invention Tannin 3, Relationship with the case of the person making the amendment Patent Applicant Address 601 Kisshoin Nishi-no-Shomon Ro-cho, Minami-ku, Kyoto City 1
4'@Place name (415) Nippon Shinyaku Co., Ltd. President Hiroshi Morishita 4, agent residence 1, Kisshoin Nishinoshimonro-cho, Minami-ku, Kyoto 601
Column 6 of the detailed description of the invention in the specification at address 4, content of amendment 6G J.

6G' Correct to.

(2) Chemical structural formula % Formula % listed on the bottom line of page 26 of the specification Correct to.

(Chemical structural formula r 9H listed on the second line from the bottom of No. 31 Specification.

``?H δG'' (4) Correct the chemical structural formula % formula % listed on page 32, line 12 of the specification.

(5) Procedural amendment to the chemical structural formula listed on page 34 @ line 8 of the specification (voluntary) 1. Indication of the case 1982 Patent Application No. 120372 2. Name of the invention Tannin 3. Person making the amendment Relationship Patent applicant address 14, Kisshoin Nishinoshomon Rocho, Minami-ku, Kyoto 601
Address Name (415) Nippon Shinyaku Co., Ltd. President Hiroshi Morishita 4, Agent Residence 14, Kisshoin Nishinoshomon Rocho, Minami-ku, Kyoto 601
Insert the sentence below the number.

[Similarly from Jiyu * 2,3.4- tri -0-
galloyl gl+cnse (yield 0.001%)
get. Colorless needle crystals (water of crystallization) m, p.

183-184°C.

PMR (acetone ds) ppm: 3.
50-4.18 (m, α, β-9CB,, -H), 4
．． 98-6.15 (m, α, β-C-m, s, a-
H).

6.98-7.19 (m, gal 1 oil -I
f), PMR not analyzed due to m1xture of α and β.

Similarly, Methyl 3.4.6-tri from elm
-0-gulloylglucose (yield 0.00
4%). Yellowish brown amorphous powder O [α) D-52,7° (C = 0.6. aceto
ne) PMR (acetone d-) ppm
3.52(3)l, s, OCIIm)
.

3.69 (IH, t, J=8Hz, C, -H),
4.1! S(III, m.

Cm H), 4.40 (2H-m, Cm H)
, 4.58 (IH, d, J=8Hz, C, -H)
, 5.37 (IH, t, J=9H2,C, -II)
.

5.56 (IH, t, J=9T1z+cl H)
, 7.04.7.07゜7.20 (e8ch 2
I-1,s, gdl 1oyl-H).

Similarly, Methyl 2,3,4.6-te from OH
tra-0-galloylglucose (yield 0.006%) is obtained. Colorless amorphous powder.

[α], +33°8° (c = 0.94. IIc
etone)PMR(&Icetone da) p
pm: 3.50 (3H, s, OCR,).

4.24-4.70 (3H, m, C,, a-H),
4.95 (IH, d, J=8Hr, C, -H),
5.35 (114, t, J=8Hz, c, -H).

5.55 (1■L t, J=9112.C4H)
-5,85 (IH, t.

J=911z, C, -Iri, 6.96.7.0? ,
7.09. 7.23 (each2IT, s,
g+(lIoy!-I()" (2) Insert the following sentence in the bottom line of page 26 of the specification.

``Similarly + 4.5- (+1-0- gal
oil quinic acid yellowish brown amorphous powder (
A yield of 0.005%) was obtained.

[α) p-116,5° (acetone, c=0.
36), MS m/s near 88 (M+) PMR (acetone-(+, ) ppm 2.
25-2.76 (411, m.

CI, CaH), 5.52 (III, (Ill,
J=8.3Hz, CmH).

5.72-5.96 (2H,m, C,,C,-41
17,05,7,09°7.16 (each 2H,
s, galloyl, I]) CMR (acetone
) ppm: 36.2 (t, CI), 38
．． 1 (kai, CI).

68.8 (d, Cs), 69.7 (d, Cs
L 72.1 (d, Cm).

74.1 (s, C,), 109.8 (d, ga
ll, C,, c, x3L120.4.121.1 (
s, gall, C, X3), 13B, 7.139
8 (s, gall, CaX3), 145.5
(+l, gall, C,, ClX3).

166.2 (s, -Coo-X3), 176.2
(-00011)G Similarly, 3.4.5-tri-0-gal
Inyl quoinic acid colorless amorphous powder (
A yield of 0.005 was obtained.

[α]D-35,5°(acetone, c=zO,
19) PMR (acetone-ds) ppm
: 2,10~2.50 (411,rn.

C,,C,-14), 4.53 (11-J,
sex, J-8, 6Hz, C5-H).

5.17 (tr4. dd, J=911z, 3
Hz, Cm H)-7,08°7.1.3 (el
Ich 2H, s, gall, H) CMR (ace
tone-da) ppm: 36.7 (Ca),
41.6 (Ct').

65.5 (Cm), 69.7 (Cm), '14.6CC
x), 75.9 (Ca).

109.9(gdll, C,, (4X2), 12
1.3. 121.7 (gall.

Cx), 13B, 3. 138.5 (g&Ill, C
), 14a5 (gall.

C,,C,X2), 165.8,166.1(-Coo
-), 176.5 (-COOH) Written amendment to the above procedure (spontaneous) 1. Indication of the case 1982 Patent Application No. 120372 2. Name of the invention Tannin 3. Person making the amendment Relationship to the case Address of the patent applicant 11-cho, 14-cho, Kisshoin-Nishinoshomon, Minami-ku, Kyoto City.Place name (415)Kuchimoto Shinyaku Co., Ltd. President and CEO: Hiroshi Mori]4, Agent residence: 14, Kisshoin-Nishinoshomon-cho, Minami-ku, Kyoto-shi. In Column 6 of Detailed Description of the Invention, Contents of Amendment (+) Specification IF, page 13, insert the following sentence before Example 3.

[The following substances were obtained in the same manner.

(Yield 0.003%) Cinnam Lanninrl Yellowish brown amorphous powder [α piece ++02. l° (c=0.99. aceto
ne) PMR (acetoned6) ppm:
2.85 (21L m, c4-H), 4.10 (
41T, hr, s, C3', 3', '3'''J''-T
I), 4.36 (IH, hr, s, C3-H)
.

4.63.4. C8, 11, 80 (4Hin Muo
ta I, s, C4', 4", 4", 'I? old
, 4.96°5.04.5.20.5.27 (
5Hin total, s, c2, 2', 2", 2",
2″!H) 6.04~6.12 (6TT, m,
CG, 6', 6", C:", 6":8"'), 6
．． 60-7.24 (15H, m, aroma-011) CM r? (acetonod6)D, O) ppm
: 36.7 (C4', 4°: 4""), 6
6.2 (C3), 72.2.72.3, 72.5 (
C3', 3''°, :;':3''''), 7G, 2 <c
2', 2", 2": 2''''), 78.6
(C2), 96.3.96.9 (C6,6',
6", 6°": 8"") (2) Insert the following sentence in the bottom line of page 36 of the specification.

"Example 14 After digesting 1.8 kg of camphor tree with 31 ml of acetone and distilling off the acetone.

Dissolved in water and partitioned several times with edyl acetate (11).

The following materials were obtained in the same manner as in Example 12.

(Yield 0.033%) KUS-9 colorless polymorphic crystal Melting point 〉300℃ [α), +102.3° (c
,=0.9') position+cetonc)PMR(DMSO
-dc) ppm: 3.76 (2H, m, C
3,3'-H), 3.80 (IH, d, J =
411z, C3'il(), 4.23 (Ill
, d, J = 411z, C4”-H) 4.43
(IH, s, C4'4-1), 4.84 (IH
, d, , J = 811z, C2-1-T)" 2 Procedural amendment voluntarily) 1. Indication of the case 1982 Patent Application No. 120372 2. Name of the invention Tannin 3. Person making the amendment Relationships Patent applicant address: 14 Kisshoin Nishinosho Monguchi-cho, Minami-ku, Kyoto, 601 Name (415) Hiroshi Morishita 4, President and CEO of Nippon Shinyaku Co., Ltd. Address of agent: 601 Kisshoin Nishinosho Monguchi-cho, Minami-ku, Kyoto Column 6 of the Detailed Description of the Invention in the Specification No. 14, Contents of Amendment (1) The following sentence is inserted after the last line of page 36 of the specification.

[Example 15 From 20 kg of Ceylon cinnamon, in substantially the same manner as above.

The following substances were obtained.

■Compd I: Yellow powder [α]. +70.
3° (acetone) Yield (0.1%) PMR (DMSO-d6,150”C) pPm:
'2.75 (211, m, C4-11) 3.75 (
LH, br, s, C3-If), 3.9
8 (III, s, C3'-II).

4.04 (11(, d, J=411z, C3”-1
1), 4.24 (Ill, tl, J= 41
1z.

II C4-II), 4.40-4.76 (211
, m, C2,4'-II), 5.38 (I
ll.

s + C2'It) CMR (acetone d6) ppln: 3B
, 0 (C4', 4") 166.5 (C3, 3')
, 71.6 (C3'), 78.2 (C2')
, 79.8 (C2) , 99.5°96.2.97
．． 9.99.4.99.9 (C6, (i', 8″:
2″)■Compd If Yellow powder [αlb
+51.1゜Yield (0.02%) PMR (acetone di,) 213m: CMR (acetone +16) that cannot be analyzed due to rotational disorder
ppm: 36.4.37.1 (C4,4", 4
″'）.

66.5 (C3,3'), 71.3 (C3"'
), 75.8 (C2''), 77.9 (
C2'), 79.4 (C2), 95.7.96.
2.98.3.99.5 (C6,6:6?678':
2''> Example 16 The following substance was obtained from 2.13 kg of chestnut bark in a manner similar to that described above.

■Con+pd X V hamamclitann
in (αlo +30.2 ° (H2O) yield (0,28%) colorless needle crystals mp, 148 °C P
M R (acetone d6) ppm: 5
．． 32. 5.3ft (Ill in Loca
l.

each s, a C1-II, βCLll
), 7.14. 7.111 (eat:b
211゜s, galloyl-11) ■Compd X Vl 3+5+2'-1ri-
0-6811oil hamamclose yield (0,
007%) Colorless acicular crystals mp, 210℃ [α]
o +29. O° (acetone -1120)
PMR (acetone d<) pPm: 5.2
0+ 5.59 (III in Lot++l.

d, J-811z, C3-1t), 5.44.
5.48 (III in total, s, t:
x C1-■, βC1-1t), 7.12.7.
16.7.20 (eaCh 211.s, Hal
loyl-11) CMR (acetone d6) ppTIl: 6
4.8.66.3.66.7.67, +1 (C5-α
, β, C2'-α, β), 73.1 (C'3-α
), 74.9 (C3-α'), 78.5 (
C2-α), 78>9 (C4-α, β), 11
1.1 (C2-β)167.5.167.2.167
．． 0 (C=O')'' to pA

Claims (1)

[Claims] The following general formula] is t-+U (R', R'' represent the same hydrogen or hydroxyl group, R*
, R4 are the same or different and represent hydrogen or a galloyl group (hereinafter abbreviated as G). ) and its methylate. (n represents 2 or 3). A compound represented by the following general formula [Peng (R', R@, R' are the same or different and represent hydrogen, methyl, or G). The following compound is represented by a cup. A compound represented by the following general formula α] - (2) (R@, R" are the same or different and represent hydrogen or G.) The following formula (4) (R1: R11, nll R14 is the same - or differently represents hydrogen or G, and R' = dihydrogen or hydroxyl group. or represents a hydroxyl group; BH, R1: T, !XI are the same or different and represent water volume or 0;
llZ compound. <R*6. R-1 is the same or different and represents hydrogen or methyl. ). <n1% R11 is different and hydrogen or R represents hydrogen or methyl. ) A novel tannin selected from the group consisting of compounds represented by