FLAVONOL

T h e s e are 3 - h y d r o x y d e r i v a t i v e of f l a v o n e s . The chemical s h i f ts of C-2

and C-3 are d r a m a t i c a l l y affected by the introduction of the 3-OH s u b s t i t u e n t
into the flavone s k e l e t o n . The C-3 s h i f t s downfield ca. 32 ppm
and C-2 and C-4 moves u p f i e l d v i a ca. 17 and ca. 5 ppm in going from f l a v o n e to f l
avonol.
A comparison of the ± 0C s h i e l d i n g data for unsubstituted flavonol
(3.390) [168] with unsubstituted flavone (3.171) [13, 98] infers the s h i f ts induced by the 3-
OH s u b s t i t u e n t s ( C - 2 , - 18.0; C-3, +31.4; C-4, - 5 . 4 ; C-5
- 3 . 9 ; C-6, - 3 . 2 ; C-8, + 0 . 2 ; C - 9 , - 4 . 7 ; C - 1 0 , - 2 . 7 ; C - l ' , + 0 . 5 ; C - 2 ' / C - 6
' , - 1 . 3 ;C - 3 1 / C - 5 ' , + 0 . 5 ' ; C - 4 ' , - 1 . 7 ppm). The chemical s h i f t s of the aryl
carbon resonances e x h i b i t resemblance in both c a t e g o r i e s of f l a v o n o i d s .
Both C-2 and C-3 are quaternary o x y - o l e f i n i c t y n e d i s p l a y i n g s i g n a l s
u s u a l l y between 133.5-151.2 ppm. Assignments of C-2 and C-3 resonances
can r e a d i l y made as C-2 u s u a l l y resonates at l o w e r f i e l d 5.0-13.0 ppm in
comparison to the C-3 resonance (Table 3.4) [ 2 1 , 3 0 , 3 8 , 5 6 , 6 1 , 9 1 , 9 7 , 1 6 8 - 1 8
8]. G e n e r a l l y the resonance appearing at 140.0-151.2 ppm. corresponds to C-2 w h i l e
that appearing at 133.5-140.0 ppm corresponds to C - 3 .
The presence of the o x y s u b s t i t u e n t at C - 2 1 p o s i t i o n does not cause
an u p f i e l d shift of the C-2 resonance but leads to s l i g h t downfield shift
( 0 . 9 - 2 . 3 ppm). The chemical shift of the C-3 also remain unaffected by
an V - o x y s u b s t i t u e n t [168].

The chemical s h i f t of c a r b o n y l resonance, in f l a v o n e s , i s i n d i c a t i v e

of the s u b s t i t u t i o n at C-5 position and is also s e n s i t i v e to d e r i v a t i z a i on
of the 3-OH group. Hence, f l a v o n o l s with u n s u b s t i t u t ed C-5 p o s i t i o n or with
a 5-methoxyl group give r i s e to an a b s o r p t i o n at 172.4±1.4 ppm whereas
c o m p a r a b l y low f i e l d position at 177.3±1.5 ppm in 5 - h y d r o x y l a t e d f l a v o n
o l s .A further u p f i e l d position of ihe C-4 resonance is noted in case of 3-acetyl
a t e d - 5 - m e t h o x y l a t e d flavonol such as 3.421 and 3.424 [ 9 1 ] .

A c y l a t i o n at C-3 ( 3 - a c e t y l k a r a n j i n , 3.402) induces s m a l l e r e f f e c ts

on ring A c a r b o n s , but causes a s i g n i f i c a n t u p f i e l d shift at C-3 ( - 5 . 5 ppm)
as well as a l a r g e downfield shift at C-2 (+10.4 ppm). This is p r o b a b ly
a result of the i n c r e a s e d e l e c t r o n e g a t i v i t y of the acyl s u b s t i t u e n t , r e l a t
i ve to hydrogen. A l l y l substitution at C-3 ( 3 - a l l y l k a r a n j i n ; 3.403) introduces
downfield s h i f t s 4.1 and 10.1 ppm of the C-3 and C-2 resonances r e s p e c t i v e l y .

However, Pomillio et_ al_. [91], in contrast to the above observ

a t i o n s , noted downfield shift 0.9 and 2.3 ppm of the C-2 in quercetin-
5 , 7 , 3 ' , 4 ' - t e t r a m e t h y l e t h e r - 3 - O - a c e t a t e (3.421) and 3.424 r e s p e c t i v
e l y . The u p f i e l d s h i f t s , 3.7 and 3.5 ppm in 3.421 whereas 4.7 and 4.7 ppm in 3.424
for C-3 and C-4 are also noted in a d d i t i o n to downfield shift 2.2 and 2.6
ppm of the C-20 in the r e s p e c t i v e c a s e .

In 5 , 7 - d i h y d r o x y l a t e d f l a v o n o l s , among C-6 and C-8 methine

r e s o n a n c e s , C-6 resonates at about 5 ppm lower f i e l d r e l a t i v e to C-8 r e s o
nance.If both C-6 and C-8 p o s i t i o n s are s u b s t i t u t e d with methoxyl groups
as in 3.433, the difference in chemical s h i f t s for C-6 and C-8 i s not so much but s t i l l s i
g n i f i c a n t ca. 3.2 ppm for r a p i d assignment [187]. S u b s t i t u t
i o n at C-8 p o s i t i o n causes s i g n i f i c n t d e s h i e l d i n g of the C-8 resonance and
C-6 absorbs almost at the same position as in 8-unsubstituted compound.
For e . g . C-6 and C-8 resonances appear at 98.7 and 94.9 ppm in 5 , 7 , 2 ' , 4 ' -
t e t r a h y d r o x y l a t e d f l a v o n o l (3.412) whereas at 98.5 and 103.9 ppm and at 98.5
and 105.8 ppm in kushenol C (3.427) [183] and kushenol G (3.428) [63] with C^q terpene
substituent at C- 8 p o s i t i o n . Similar X O C s h i e l d i n g behaviours a r e shown by b r
o u s s o f l a v o n o l C (3.439) and b r o u s s o f l a v o n o l A (3.440) having C- 8 i s o p r
e n y l substituent [188].
G l e p i d o t i n A (3.404) r e p r e s e n t s an e x c e p t i o n to the above menti o n e d 13 C
s h i e l d i n g b e h a v i o u r for 8 - C - a l k y l s u b s t i t u t e d 5 , 7 - d i h y d r o x y l a t
e d flavono] as C- 8 absorbs at s i g n i f i c a n t l y high f i e l d position, 93.0 ppm i n s p i t
e of the fact that C- 8 bears a prenyl substituent. The reason for s u c h unusual b e h a v i o u
r of the C- 8 resonance is a l s o not mentioned [ 3 8 ] .
M a s t e r o v a et_ a l . reported the c h a r a c t e r i z a t i o n of a flavonol
a l k a l o i d (3.411) having 3 - m e t h y l - 2 - o x o - p y r r o l i d i n y l substituent at C- 8 p
o s i t i on w h i c h lead to the appearance of C- 8 resonance at s i g n i f i c a n t l y low f i e
ld 13 p o s i t i o n 106.8 ppm. Thus a comparison of the C chemical shift of 3.411 w i t h
3.406 e x h i b i t 13.4 ppm oc - e f f e c t on C- 8 resonance and n e g l i g i b le
meta effect on C- 6 resonance.
In furanoflavonols, 3.401 to 3.403 , methine resonances of the furan ring occur within narrow
l i m i t s 145.3±1.1 for oxymethine and 105.0±1.0 ppm for nonoxygenated methine. The
furan ring s u b s t i t u t e d ring A resonances C- 7 and C- 8 in these compounds appear at
157.6±0.3 and 117±0.4 ppm [172].Thus C- 8 absorbs almost at the same p o s i t i o n as in
unsubstituted flavonol (3.390) [168]. It may be perhaps due to almost equal ipso effect of the
a l k y l s u b s t i t u t i o n and ortho effect of the o x y s u b s t i t u t i o n of the furan ring.
Both of these e f f e c t s n u l l i f y each other.