Flavonoids from seeds of Maclura aurantiaca growing in Georgia

Full text of DOI:10.1007/s10600-009-9243-z

Chemistry of Natural Compounds, Vol. 45, No. 1, 2009
FLAVONOIDS FROM SEEDS OF Maclura aurantiaca
GROWING IN GEORGIA
*
N. Sh. Kavtaradze, M. D. Alaniya,
UDC 547.972
and K. G. Shalashvili
Nutt. is known to contain biologically active compounds [1-4]. The flavonoid and lipid
Maclura aurantiaca
compositions of fruit pulp, which has antitumor activity, have been studied [2, 5]. Flavonoids from seeds of
M. aurantiaca
growing in Georgia have not been studied. Column chromatography of the aqueous alcohol (80%) extract of defatted seeds
isolated total phenolic compounds with 0.28% flavonoid content. Column chromatography over silica gel isolated three
compounds from the total extract.
Compounds 1 and 2 did not give a Synod reaction [6]. Absorption maxima in the UV spectra were typical of
isoflavones. Compound 3 was a flavonol glycoside.
Compound 1, mp 188-191°C (CHCl ), UV spectrum (CH OH, λ , nm): 270. IR spectrum (KBr, ν, cm−1):
3
3
max
3417 (–OH), 3070, 2969, 2923, 2854 (aliphatic –CH and CH ), 1643 (>C=O), 1573, 1519 (aromatic CH=CH), 1434, 1365
2
3
[C–(CH ) ], 1326 (>C–OH). Acetyl derivative of 1, mp 165-167°C. The analytical results indicated that 1 was osajin [1].
3 2
Compound 2, mp 173-175°C (CHCl ). UV spectrum (CH OH, λ , nm): 270. IR spectrum (KBr, ν, cm−1):
3
3
max
3425 (–OH), 3070, 2969, 2907, 2854 (aliphatic –CH and CH ), 1643 (>C=O), 1565, 1519 (aromatic CH=CH), 1442, 1380
2
3
[C–(CH ) ], 1326 (>C–OH). Acetylation product of 2, mp 127-130°C (CHCl ). The melting point of the acetate product
3 2
3
differed from that of pomiferin acetate (134.5°C) [1]. This may have been due to the effect of the crystallization medium or its
conformational features.
13
Table 1 lists PMR and C NMR analysis of correlation spectra. It can be seen that these compounds differ in the
structure of ring B. Compound 1 is unsubstituted at position C-3′ whereas it has a hydroxyl in the 2-position. This was
confirmed by the singlet for C-2′ at 7.05 ppm in the PMR spectrum and the resonance at 147.0 ppm corresponding to C-3′ as
a result of a weak-field shift of this resonance from 116.0 to 147.0 ppm compared with 1.
Methyls on the pyran ring resonated at 28.3-28.0 ppm; aliphatic, at stronger field of 26.4-26.5 and 17.2-17.0 ppm;
correlating atoms C-3′″ and C-2′″. The CH C atom at 22.4 ppm correlated with C-2′″, C-3′″, and C-7.
2
13
PMR and C NMR correlation spectra agreed completely with the structures of osajin (1) and pomiferin (2) [7], the
structures of which were also established by chemical transformation [1, 2] and crystallographic analysis [8].
Compound 3 was needle-like yellow crystals, mp 226-228°C (alcohol). UV spectrum (C H OH, λ , nm): 355, 265;
2
5
max
+CH COONa: 367, 270. IR spectrum (KBr, ν, cm−1): 3400 (–OH), 1640 (>C=O), 1575, 1540, 1520 (aromatic CH=CH).
3
Compound 3 was hydrolyzed by acid and base to form the aglycon, which was characterized as kaempferol. PC of the
carbohydrate part detected L-rhamnose, which was bonded to C-7. Thus, 3 was identified as kaempferol-7- -α-L-rhamnoside
O
[9].
I. Kutateladze Institute of Pharmaceutical Chemistry, 0159, Georgia, Tbilisi, ul. P. Saradzhishvili, 36, fax:
(995) 32 52 00 23, e-mail: merialania@yahoo.com. Translatedfrom KhimiyaPrirodnykh Soedinenii, No. 1, pp. 79-80, January-
February, 2009. Original article submitted June 30, 2008.
0009-3130/09/4501-0089 ©2009 Springer Science+Business Media, Inc.
89

TABLE 1. Chemical Shifts of 1 and 2 (CD3OD, δ, ppm)
1
2
C atom
δH
δC
HMBC
3, 4, 9
δH
δC
HMBC
3, 4, 9
2
3
4
5
6
7
8
9
10
1′
2′
3′
4′
5′
6′
1″
2″
3″
1′″
2′″
3′″
Me
8.12, s
154.4
125.0
182.6
158.8
115.0
157.5
102.5
152.3
116.7
123.0
131.5
116.0
158.5
116.0
131.5
115.4
128.0
80.2
8.06, s
154.4
125.0
182.6
159.0
114.8
157.5
102.5
152.2
116.6
124.0
117.3
147.0
147.5
116.2
121.5
115.5
128.3
80.0
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
7.39, d
6.86, d
-
6.86, d
7.39, d
6.75, d
5.70, d
-
3.33, m
5.20, m
-
1.48×2, s
1.68, s
1.82, s
1′, 3′, 4′
1′, 4′
7.05, s
1′, 3′, 4′
-
-
6′, 4′
5′, 4′
3″, 8, 7
8, 3″, Me
6.83, d
6.85, d
6.74
5.68
-
3.31, m
5.20
-
6′, 4′
5′, 4′, 1′
22.4
2′″, 3′″, 7
1′″, 3′″, Me
22.1
2′″, 3′″, 7
1′″, 3′″, Me
123.0
131.5
28.3×2
26.4
123.0
131.5
28.0×2
26.5
3″, 2″
3′″, 2′″, Me
3′″, 2′″, Me
1.46×2
1.67
1.82
3″, 2″
3′″, 2′″, Me
3′″, 2′″, Me
17.2
17.0
REFERENCES
1.
2.
E. D. Walter, M. L. Wolfrom, and W. W. Hess, J. Am. Chem. Soc., 60, 574 (1938).
M. L. Wolfrom, F. L. Benton, A. S. Gregory, W. W. Hess, J. E. Mahan, and P. W. Morgan, J. Am. Chem. Soc., 61,
2832 (1939).
3.
4.
K. G. Lewis, J. Am. Chem. Soc., 83, 2330 (1961).
G. K. Nikonov, L. N. Safronich, and N. Sh. Akhmedkhodzhaev, Phenolic Compounds and Their Physiologial
Properties [in Russian], Nauka, Alma-Ata (1973), p. 127.
5.
6.
7.
M. A. Bitadze, Ts. M. Dalakishvili, E. P. Kemertelidze, and M. D. Gedevanishvili, Khim.-farm. Zh., 7, 21 (1993).
V. A. Geissman, Biochemical Methods of Plant Analysis [in Russian], Moscow (1960), p. 453.
W. L. Whaley, J. D. Rummel, E. Zemenu, W. Li, P. Yang, B. C. Rodgers, J. Bailey, C. L. Moody, D. V. Huhman,
C. G.-A. Maier, L. W. Sumner, and S. D. Starnes, Chem. Educ., 12, No. 3, 179 (2007).
M. Liskova, J. Marek, D. Jankovska, L. Sukupova, M. Zemlicka, and J. Vanco, Acta Crystallogr. Sect. E: Struct.
Rep. Online, 61, 1848 (2005).
8.
9.
M. D. Alaniya, N. F. Komissarenko, and E. P. Kemertelidze, Soobshch. Akad. Nauk GSSR, 68, 357 (1972).
90