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Phyrochemistry, Vol. 33, No. 4, pp. 909 911, 1993 003 l--9422/93 $6.00 + 0.

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Printed in Great Britain. Q 1993 Pergamon Press Ltd

TWO 2’,4’,6’-TRIOXYGENATED FLAVANONES FROM ARTOCARPUS


HETEROPH YLLUS*

CHAI-MING Lu and CHUN-NAN LIN

Natural Products Research Center, Kaohsiung Medical College, Taiwan 807, R.O.C.

(Received 18 Nooember 1992)

Key Word Index-Artocarpus heterophyllus; Moraceae; 2’,4’,6’-trioxygenated flavanones;


prenylflavanone; 5-hydroxy-7,2’,4’,6’-tetramethoxflavanone; 8-(y,y-dimethylallyl)Shydroxy-7,2’,4’,6’-
tetramethoxytlavanone.

Abstract-Two novel 2’,4’,6’-trioxygenated flavanones, heteroflavanones A and B, were isolated from the root bark of
Artocarpus heterophyllus. Their structures were elucidated as 5-hydroxy-7,2’,4’,6’-tetramethoxyllavanone and 8-(y,y-
dimethylallyl)S-hydroxy-7,2’,4’,6’-tetramethoxyflavanone.

INTRODUCTION

In previous papers [l-4], we reported a series of pre-


nylflavonoids from the root bark of Artocarpus communis.
In continuation of this work, two novel 2’,4’,6’-
trioxygenated flavanones were obtained from the root
bark of Artocarpus heterophyllus. The novel 2’,4’,6’-
trioxygenated flavanones, sophraflavanone D,E and ken-
1 R=H
usanone B-E have recently been isolated and character- 2 R=-CHEXH=C(M~)Z
ized from Echinosophoru koreensis [S, 61. We now de-
scribe the structure determination of these two 2’,4’,6’-
trimethoxylated flavanones.
m/z 168 corresponding to a phloroglucinol ion [S, 6). The
above fragment ions suggest that 1 has a 2’,4’,6’-
RFSC’LTS AND DISCUSSION
trioxygenated B ring and all three hydroxyl groups are
Compound 1, C,,H,,O,, mp 184”, has similar UV methoxylated [S, 63. Hence, heteroflavanone A is charac-
maxima to sophraflavanone E [S] and the AK&-induced terized as 5-hydroxy-7,2’,4’,6’-tetramethoxyflavanone (1).
bathochromic shift suggest 1 to be a 5-hydroxy-7,2’,4’,6’- In the 13C NMR spectrum of 1 (Table l), the chemical
tetraoxygenated flavanone. The IR spectrum of 1 showed shift values of C-4 to C-10 were almost superimposable
a strong absorption band at 1645 cm- 1 due to the with those of corresponding data for 5-hydroxy-7,4’-
chelated carbonyl. The ‘H NMR spectrum showed three dimethoxyllavanone [8] and the assignment of carbon
one-proton double doublets at 6 5.98 (J = 14,3 Hz), 3.92 signals of C-2 to C-3 and C-l’ to C-6’ were obtained bv
(J = 17, 14 Hz) and 2.50 (J = 17,3 Hz), attributed to the comparison with those of corresponding data for kenus-
H-2, H-3ax and H3eq of a flavanone [S, 61, four methoxyl anone E (3) [6] and on the basis of methylation-induced
signals at 63.78,3.80 (2s) and 3.83, a pair of meta-coupled shifts [8]. The signals observed supported the structure
doublets at 66.02, 6.03 (J = 2.2 Hz) assignable to H-6 characterized as 1.
and/or H-8, a chelated phenolic signal at 6 12.23 (5-OH) Compound 2, mp 145-147”, and similar UV maxima to
and a two proton singlet at 6 6.16 attributed to protons in sophraflavanone E [S] and an AlCl,-induced batho-
the B ring nucleus. In EI mass spectrum of 1, a [M] ’ peak chromic shift suggest 2 is also a 5-hydroxy-7,2’,4’,6’-
at m/z 360 and significant peaks at m/z 194, 179 (base tetraoxygenated flavanone. The IR spectrum showed a
peak) [194-Me]+, 167,166,151 and 135 were attributed chelated carbonyl at 1635 cm-‘. The ‘H NMR spectrum
to typical retro-Diels-Alder fragmentation [7]. The EI of 2 showed typical H-2 and H-3 signals at 65.91 (dd, J
mass spectrum also showed a characteristic fragment at = 17,3 Hz, H-2), 3.87 (cad,J = 17, 14 Hz, H3ax) and
2.50 (dd, J = 17,3 Hz, H-3eq) of a flavanone skeleton [S, 6-J,
four methoxy signals at 63.79 (29), 3.83, 3.84 and three
*Part 5 in the series ‘The Bioactive Principle-sof Formosan aromatic proton signals at 66.05 (lH, s) and 6.15 (2H, s).
Artocarpus Species’. For Part 3 see ref. [4]. The ‘HNMR of 2 also showed the presence of a y,y-

909
910 CHAI-MINGLu and CHUN-NAN LIN

Table 1. 13C NMR chemical shifts of l*, 2* and


3 Fl

C 1t 2t 3$

2 12.0 71.7(d) 73.7


3 40.6 40.7(t) 41.1
4 198.8 199.4(s) 199.3
5 164.8” 163.1(s) 163.7
6 95.2 92.2(d) 96.6
Fig. 1. Long-range coupling in the 13C_lH long-range COSY
7 168.0 165.6(s) 166.0
of heteroflavanone B.
8 94.3 109.0(s) 109.1
9 164.7” 160.9(s) 161.1
10 103.7 103.5(s) 103.6
1’ 106.8 107.6(s) 104.9
158.6
B(2). Since the specific optical rotations of 1 and 2 are
2’,6 160.6 160.7(s)
3’,5 91.6 94.6 positive, the configuration at C-2 of 1 and 2 may be
91.5(d)
4 162.6 162.3(s) 162.3 different to those of other natural flavanones [7]. In this
1” 22.1(t) 22.2 study we obtained two novel 2’,4’,6’-trioxygenated flavan-
2” 123.2(d) 123.4 ones for the first time from a member of the Moraceae,
3” 131.3(s) 131.3 although such compounds have recently been isolated
4” 26.3(q) 25.9 from a member of the Leguminosae, Echinosophora kor-
5” 17%) 17.7 eensis [S, 6-J.
OMe 55.9 55.8 55.3
56.0 56.3 x 3 56.4
56.3 x 2 EXPERIMENTAL

Plant material, extraction and isolation. Root bark of


*The number of directly attached protons to
Artocarpus heterophyllus 1 kg was collected at Ping-Tung
each individual carbon was verified with DEPT
pulse sequence. Hsien, Taiwan, R.O.C., during July 1992, and chipped
tMeasured in CDCl,. and extracted with acetone at room temp. in a closed
$Measured in acetone-d,. container several times. The acetone extracts were chro-
‘These signals may be reversed in each column. matographed on silica gel. Elution with cyclohexane-
CHCI, and repeated chromatography yielded 1 and 2 as
colourless needles.
Compound 1 (heteroflauanone A). Mp 184”, [a];”
dimethylallyl group [S 1.54 (Me), 1.61 (Me), 3.13 (W, br d, + 7.0”(CHCI,; c O.lO), UV nE:F” nm (log E): 333 (3.60),
CH,) and 5.14 (IH, m, CH=)] and chelated hydroxyl 285 (4.25), 228 (sh) (4.42), 210 (4.72); MeOH-AlCl,: 362,
signal at 612.34 (5-OH). The ET mass spectrum of 2 310, 290, 224 (sh), 210. ‘HNMR (CDCI,): see text.
showed a molecular ion peak at m/z 428 and significant 13CNMR (CDCI,): see Table 1. ElMS (direct inlet) 70 eV,
peaks at m/z 194, 179 (base peak), 164 and 148, attributed calcd for C,gHzoO,: 360.1210. Found (MS): 360.1185.
to typical retro-Diels-Alder fragmentation [7]. The EI Compound 2 (heteroflauanone B). Mp 145 N 147”, [a];
mass spectrum of 2 also showed a characteristic fragment + 64.0” (CHCl,; c O.lO), UV ;L:$‘” nm (log E): 340 (3.70),
at m/z 168 corresponding to a phloroglucinol ion [5,6]. 290 (4.26), 230 (sh) (4.40), 211 (4.69); MeOH-AlCl,: 393,
The base peak at m/z 179 derived from the A or B ring 312,225 (sh), 211. ‘H NMR (CDCl,): see text. 13C NMR
showed that the A ring had one hydroxyl, one methoxyl (CDCl,): see Table 1. EIMS calcd for C,,H,,O+
and an alkyl group 15, 61. The above fragment ions and 428.1833. Found (MS): 428.1810.
‘HNMR spectrum, together with the presence of a
bathochromic shift with AlCl, in the UV spectrum Acknowledgements-This work was supported, in part,
suggest that 2 is 8-(y,y-dimethylallyl)5-hydroxy- by grants from the National Science Council of the
7,2’,4’,6’-tetramethoxyflavanone [S, 6, 93. Based on the Republic of China (NSC 82-0420-B037-008-M 13) and the
above results, the proton signal at 66.05 (s) was assigned National Research Institute of Chinese Medicine, Taipei,
to H-6 and the two proton singlets at 66.15 were assigned Taiwan, R.O.C.
to H-3’ and H-5’. In the 13C NMR spectrum of 2 (Table
l), the chemical shift values of C-4 to C-IO, except for C-6
showed upfield shift by comparison with that of corres-
REFERENCES
ponding data for kenusanone E (3), C-l” to C-5”, C-2 to
C-3 and C-l’ to C-6’ were almost superimposable on 1. Lin, C. N. and Shieh, W. L. (1991) Phytochemistry 30,
those of corresponding data for kenusanone E (3) and 1 1669.
(Table l), respectively. The assignment of carbon signals 2. Shieh, W. L. and Lin, C. N. (1992) Phytochemistry 31,
of 2 was also confirmed by ‘H-13C long-range COSY 364.
(Fig. 1). Therefore, the carbon signals observed sup- 3. Lin, C. N. and Shieh, W. L. (1992) Phytochemistry 31,
ported the structure characterized as heteroflavanone 2563.
Flavanones from Artocarpus heterophyllus 911

4. Lin, C. N. and Shieh, W. L. (1992) Phytochemistry 31, Flavonoids (Harbome, J. B., Mabry, T. J. and Mabry,
2922. H., eds), Ch. 3. Academic Press, New York.
5. Iinuma, M., Ohyama, M., Tanaka, T., Mizuno, M. and 8. Agrawal, P. K. and Rastogi, R. P. (1981) Heterocycles
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Hong, S.-K. (1992) Phytochemistry 31, 2855. (1980) Tetrahedron Lett. 21, 641.
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