CHAPTER

THREE

FLAVONOIDS
PAW AN K . A G R A W A L ,
and

3.1

In

plants,

sugar)

occur

atoms

in their

tion.

Each

by

tion
are

flavonoid
variety

carbon

one

of

unit

the

an

utilizes

ring C followed
one,

section

ordinary
by

these

chromone

as

chromone

skeleton

the

possess

third

via

an

attached

fifteen

in a C g - C ^ - C g
aromatic

heterocyclic

oxygen atom.

rings
ring

The

for

the

r i n g s A and

numerals

for

-C

the

carbon

configuraare

via

linked
cycliza-

aromatic

heterocyclic ring as ring C . The

parent
as

keto

of f l a v o n e a r e

termed

substituent

category

3-phenylchromanone
3-phenylchromanone

or ' D i h y d r o f l a v o n e s ' .
'Flavanonol'

or

of

4-position

flavonoids

designated
as

as

'Flavonol'

at

C-3

but

rings

numbering

starting

ring

(see

from

Chapter

constitutes the
skeleton

benzopyrelium ion

which

to

and

similarly
are

2-phenyl

possess

'Flavones'. The

position

flavonoids lack

Similarly,

resulting

named

2-phenyl
3-hydroxy

flavones

having

as ' 3-methoxy-

respectively.

as

with

parent
such

3-hydroxy

'Dihydroflavonol' .

Flavanone

at

Those

are

'3-prenylatedflavone'

Another

group

skeleton.
such

or

possess

These

primed

flavone'

and

ring.

numerals

isoprenyl

as

arranged

ring

or

having

are

- B and

methoxy

hence

these

without

A l l contain

1.2).

Usually

derivative

flavonoids

forms.

form

r i n g A and

(i.e.

structural

aromatic

aromatic

l a b e l l e d as ring A and

scheme

aglycones

of

which

THAKUR

C . BANSAL

INTRODUCTION

b a s i c nucleus and

Cg r e p r e s e n t s

three
with

in

RAGHUNATH S .

MAHESH

are

the

2,3-olefinic

carbon

skeleton.

designated

substituted

as

flavanone

Anthocyanidin lack

structure.

Flavanonol

with

bond

and

Flavonoids
'Flavanones'
are
4-keto

termed
group

96

3-prenylatedflavone
The
have
for

been
the

occurrence
reviewed

and

Anthocyanidin
distribution

[1-4].

characterization

The

of f r e e

ultraviolet,

of f l a v o n o i d s h a v e

flavonoid aglycones in

NMR a n d

mass

been also discussed

nature

spectroscopy
[2,3,5-9].

13
T h e e a r l i e s t r e p o r t of a
C NMR s t u d y of a f l a v o n o i d a g l y c o n e
a p p e a r s t o b e t h a t of J o s e p h - N a t h a n ert c d . [ 1 0 ] i n w h i c h a c o m p l e t e a s s i g n 13
ment of t h e s p e c t r u m
of f l a v o n e i t s e l f
was made. Since then,
C NMR
s p e c t r o s c o p y h a s b e e n w i d e l y e m p l o y e d f o r t h e c h a r a c t e r i z a t i o n of v a r i o u s
13
c a t e g o r i e s a n d s u b c a t e g o r i e s of f l a v o n o i d s . T h e
C shielding data
reported
13
upto

1980

have

published
tabulated

also

upto
and

been

1986

for

discussed

compiled
the

above

in this

possess

carbon-',

of

forms

each

of

the

flavanone

acquire

orientation

().

nances:

oxymethine

(C-4).
ponding

an

These

The
the
in

absorb

2'-

6'-oxy

and

at

shift

C-2'
and

of
and

shielding

categories

as

the

centre

but
at

of

information

flavonoids

of

most
C-2

ring C i s ,

parent
the

71.3-80.3,

39.5-46.4

the
C-6'

C-2

(Table 3.1)

exert

are

whereas

2' ,6'-dioxysubstituted

and

it
at

Since

isomeric
occurring

pseudoequatorial

(C-3)

of

three

and

reso-

carbonyl

186.4-198.5

corres-

[11-74].

dependence

positions as

flavanones

in

composed

methylene

two

naturally

position
thus

skeleton.

asymmetry,

of

aliphatic

C-4 respectively

6'-unsubstituted

substituted

an

between

chemical

substitution

substituent

heterocyclic

to C - 2 , C - 3 and

is

possible

(C-2),

FLAVANONES

molecule
are

phenyl

The

mentioned

2-phenylchromanone

structure

flavanones

The

chapter.
3.2

These

[4,9 ] .

particularly

resonates
8

at

75.41.6

flavanones.

Thus

upon

S 79.01.5
in

2 -

or

presence

97
of

2'-

and

or

4.51.0

ppm
13

of

son

of

tives.

the

C-2

at

shifts

for

resonance

74.9,

substituent

the

Hence

C - 2 resonance

due

The
or

of

flavanones,

p o s i t i o n 194.5

[59].

involvement

the

hydroxyl

shift

of

(3.5).
case

of

or

later

the

hence

as

interactions

for
in

in

the

existence

infering

of

in

5-hydroxy,
however

it

is

(3.2)
in

ppm

(3.9)

noted

2'-acetoxy

for

and

2'-

be

shift

in

7,8,3',
lowfield

C-4

ppm

bond

resonance

because

of

intractions)

the

of

of

of

at

the

The

same

loss

(C-4)

and

shift

[11,17].

The

with

chemical

to

by

resonance

(187.4-191.4

are

ppm
13

position

shielding

flavanones

are

comparison

(3.40) and

hydrogen

responsible

upfield
C

its

in

in comparison

data

given

of

in

chemical

5-methyl

at S 1 8 9 . 2

in

5-methoxy

intramolecular

The

whereas

i n c a s e of l a t e r

C-4

position

5-8

the

197.3

C-4 in

flavanones

5-acetoxy

3.40

except

appreciably

former

5-acetoxy

and

absence

5-hydroxy-7-methoxyflavanone

at

examplified

the

5-unsubstituted

a comparison

5-hydroxyflavanone.

at S 1 9 6 . 5

upfield

by

downfield

absorption

of

flavanones,

of

substituent

and

at

hydrogen

and

almost

upon

case

195.6-197.3

case

ppm

5-methoxy

C-4 absorbs

7.3

been

6 189.7-191.7

evident

flavanones.

can

In

resonates

5-hydroxy - 7,4'-dimethoxyflavanone

The

revealing

it

position

This

5-methoxy

respective

for

position.

5-hydroxylated

absorbs

to

(3.41).

in

7.3

comparison

shift

has

2'-hydroxy,

between

5-hydroxyl

carbonyl

3.1,

shielding

exhibits dependence

where

6 190.0

5-unsubstituted

several

of

C-5

absorbs

of

for

(C-4)
at

(3.80)

shift

Table

the

at

flavanones,

bond

(3.2)
(3.7),

ppm

deshielded

absorbs

ppm)

7-methoxyflavanone

7-methoxy-2'-hydroxyflavanone

chelation (intramolecular

presence

5-acetoxy

deriva-

4.6

7-methoxyflavanone

C-4

2'-oxy

and

C-5 position.

C-4 in
The

due t o

in

at

compari-

4.6

However,

appreciable

its

its

the

7-methoxy-2 -methoxyflavanone

resonance
flavanone

at

in

and

by

about

and

resonance

4'-tetrahydroxy

absorbs

flavanone

shift

(3.8)

peri-substituent

C-4

exemplified

79.9

in

upfield

[11].

carbonyl

presence

to

at

75.1

appreciable

can be

7-methoxy

and

4.8,

methoxy substituent

This

absorbs

75.1

7-methoxy-2'-acetoxyflavanone
respectively.

causes

C-2 resonance.

chemical

The

whereas

6'-oxy

ether

3.41,

to the

thus
former

[36].
The
dence

upon

upfield

chemical
the

shifted

5-methoxylated
of

hydrogen

electron

in
or

bond

density

shift

of

substitution

the
in

C-3 resonance
aromatic

5-hydroxylated
5-acetoxylated
interactions

on t h e

flavanones
flavanones

between

C-2 carbon

rings

atom.

5-OH

does
but

not
get

relative

show

to

[11,16,36].
and

any

depen-

slightly,(1-2

carbonyl

ppm)

5-unsubstituted,
Hence
group

existence
enhance

98
x

The

NMR s i g n a l s

unsubstituted
flavanone (3.1) were assigned
13
b y P e l t e r et_ a l . [ 1 1 ] b y c o m p a r i s o n o f
C c h e m i c a l s h i f t s with other monoand
d i s u b s t i t u t e d f l a v a n o n e d e r i v a t i v e s . T h e 13 C s i g n a l a s s i g n m e n t s w e r e ,

moreover,

confirmed

C-2'

and

C-5'

respectively

of

the

C-3'

of

by

the

impose

with

resonances

electron

each

the

Yb(Fod)3

aryl

ring

other

the

para

para

at h i g h f i e l d p o s i t i o n r e l a t i v e

carbonyl

unsubstituted

ring

and

unsubstituted

ring A

with

are

not

analogously

substitution

resonances.

Several flavanones

tuted

ring B .

130.4
at

C-l'

ppm.

Two

high

field

lowfield

to

position

corresponds

intensity

in

the

in

(for

aryl
due

to

resonances
appear

the

to

3.16-3.32)

C-4')

shift

resonances.
C-3'

ring A

possess

appear
are

being

the

intense

C-5'

and

remaining

between

range

and

that

range

is

resonance

at

due

125.8-

prominent,
relatively

The signal with

chemical shift

and

unsubsti-

whereas

Usually

C - 6 ' resonances.

mentioned

in

indicate

C s h i e l d i n g of r i n g

at S 1 3 8 - 1 4 0 . 2

and

chemical

corresponds

the

flavanones

(3.1)

substituents
13

affect

flavanones

substituted

flavanone

3.1-3.6,

C-3'/C-5'

to C - 2 ' and

above

not

e.g.

carbon

ring

by

resonates

this

two

the

ring C

of r i n g A s u b s t i t u t e d

unsubstituted

affected

resonance

signals

corresponding

super-

perhaps

C - 6 and C - 8

and

carbons

d o not

Among

position

The

C-6'

aryl

(3.1)

signals.

(C-4).

similarly

in ring A does

resonances ( C - 2 1/ C - 6 ' ,

methine
each

The

six

lowfield

to

six

The

to C - 5 r e s o n a n c e .

having

resonances

equivalent

represent

to
at

[12,13].

o x y g e n f u n c t i o n of b e n z o p y r o n e

having

ring

rise

13 C c h e m i c a l s h i f t s

A c o m p a r i s o n of

that

magnetically

studies

of Ring A i n f l a v a n o n e

give

to t h e

shift

resonances

ring A , C-7 absorbs

by

and

hence

induced

are

four

s i x carbons

of

withdrawal

being ortho

the

therefore,

ring B . A l l the

methine
as

for

the

normal

cc C - 4 '

reso-

nance .
Most
at

C-5

of

ring A in

by

and

Wagner

lowerfield

of

the

C-7
case

eX_ al_.
than

naturally

positions,
of

pinocembrin

who

reported

C - 8 methine

aring

between S 162.9-166.7,

gned

to

C-7

mentioned
as

an

ppm

that

assignments

long range
[54].

whereas

example

are

in

studies

deshielded

and
the
at

(3.3)
the

are

of

of

to

position

hydroxy
the

importance.

appearance

of

substituents

carbon
These

C-6 methine

resonances
were

made

resonance

among C - 5 , C - 7 , C - 9 o x y a r y l c a r b o n s
resonance

high
by

long range

lead

bear

assignments

field

at

most

position

lowfield
is

5,7-dihydroxyflavanone,

confirmed

coupling and

These

occurring flavanones

therefore,

Shirataki

s e l e c t i v e proton

conclude
than

et^ j d .

C-8

that

due
taking
on

above

naringenin
b a s i s of

(3.36)
13 C - 1

(LSPD)

studies

decoupling
These

assi-

C - 9 . The

the

C-6 resonance

resonance.

position was
to

at

appe-

absorbs
studies

at
also

about
lead

99
to

revise

the

earlier

sophoraflavanone

proposed

structures

for

sophoraflavanone

euchrestaflavanone

A [65], euchrstaflavanone

euchrestaflavanone [73]

and

their

3-95,

respectively.

3.109

resonance
0.3
bond
these

[37],

and

3.110

in

all

due to
13
1
C-

one

-effect

It

(7.2-7.3

appears

to

(geranyl)

at

Hz)

with

108.60.4

of

these

cases.

the

3,3-dimethylallyl
substitution.

unsubstituted
Substitution

Hufford
flavanone

and

from

netin

(3.21)

benzyl
tuted
tive

and

C - 6 and

studies

substituent
C - 6 and

(3.48)

of

in

Ichino

Menthyl

substituent

cases.
most

The

of

in

as

The

that

C-6

both

in

C - 6 and

prenylatednaringenin

having

ppm

is

C-6

in

holds

substi-

in the

respec-

and

the

96.8.

Thus

unaffected
chemical

true for

ortho-hydroxy-benzyl
0.9

isochama-

benzyl

remain

between

at

chemical

ortho-hydroxy-

The

107.2

C-8 absorbs

characterized

by

shifts

dichamanetin
substituent

ppm

monoterpene

(3.23)

cases,

substituted

and

chemical

distinct

of

upfield

and

at

posi-

to

the

C-8

resonance

ppm

ppm

in orientation

p o s i t i o n i s not

0.6

nosition

96.8

an a p p r o p r i a t e

absorb

C-8

and

of

Similar

p-menthene

isolinderatone

95.8

difference
but

[48].
at

C - 6 at
shift

C-8 resonances

in which C - 6 absorbs

which

at S 95.9

This

substitu-

the

[24]. Both

methine

Undertone

ppm

(3.59)

that

alter

(5108.6).

substituent
at

in
ppm

s e r i e s of C - b e n z y l a t e d
13 C NMR s p e c t r o s c o p y

in

and

difference

having

have

110.7

absorb

1 ppm.

C-8

12.8

determined.

respectively.

aryl

The

about

atom
be

compounds

108.2

which

a consequence

menthyl

ance of C - 6 r e s o n a n c e

(3.101)

[25]

difference

probably

substituent

in

namely

a t 111.8 a n d

The

about

flavanone

et^ a K

flavanones

8 absorbs

position.

C-6 resonance

stituted

at

unsubstituted

C-8 positions,
to

carbon
readily

isomeric

C-6 resonances

the

meta

are

group.

markedly

successfully

C-8 position
appear

and

bibenzylated

tion r e l a t i v e

fact

and
3.69,

(E)-3,7-dimethyl-2,2-octa-

isolated

used

(3.31)

C-8 again remains

C - 6 and

the

3.73,

demonstrated

not

methine
C-8 thus

and

C - 6 and

C-8

shift

for

both

at

C-8 resonances

the

as

revealing

or
also

does

coworkers have

chamae

chamanetin

whereas

chemical

of

hydroxyl

thus

of C - b e n z y l a t i o n i n t h e s e

substituent

case

the

site

C - 6 or

C-5

(prenyl)

These

aromatic

at

his

Uvaria

in e s t a b l i s h i n g

because

ppm

t i o n of C - 8 i n 5 , 7 - d i h y d r o x y f l a v a n o n e s ,
shift

is

structures

these compounds a p p e a r s as d o u b l e doublet at 96.5

b o n d 13 C -1 c o u p l i n g ( 1 5 9 . 8 - 1 6 1 . 9 H z ) w i t h H - 6 a n d t h r e e

coupling

due

establish

of

compounds

dienyl

to

[53],
C

at

reason

hence

in

C-

respective

seems

of t h e
for

sub-

(3.25).

to

be

isopropyl

the

appear-

evident.

107.4

situation
lowerfield

and

exists
than

106.6
in

in

6,8-di-

kushenol

C-8 resonance

[61].

C--3'
C--4'

C--5'

11

C--6' Ref.

94.,5 161..7 101..9 139.,5 125..6 128.,5 128..5 128.,5 125..6 21

94., 4 160.,3 101..7 139.,0 126.,6 128.,6 128..6 128. 6 126..6 20

166.,0
165.,2
164.,7

43.,7 195.,8 160.,9 106,.5

79.,5

78., 4 42.,2 196.,4 160.,0 102,.1

42.,3 196.,0 161.,0 103,.6

79.,8

C+D

D
C

3.,16

3.,17

3. 18

3. 18

78.,4

79.,5

78.,6

109,.8 165.,5 100.,9 162.,8 114..3 136.2

127..6 121.,7 150.,3 121. 7 127..6 11

90.,9 161..4 103..1 139.,0 126..3 128.,9 129..1 128. 9 126..3 20

44.,8 189.,8 128 ,.5 112,.4 165.,4 112.,9 158.,1 115..9 138.,9 125..7 128.,8 130.,4 128. 8 125..7 19

43.,9 190.,2 128.,4 109,.8 165.,8 100.,7 163.,2 114..6 130.,6 127..5 113.,9 159..6 113. 9 127..5 11

43.,1 189.,5 127.9

44.,2 190.,4 128.,5 110,.2 166., 4 101.,4 164..0 115..2 130.,0 128..5 115.,8 158..6 115. 8 128..5 11

3.,15

44., 1 189.,9 128.,4 109,.9 165.,8 100.,8 163., 1 114..6 140.,2 111..7 159., 7 113,.7 129. 6 118..1 11

3.,14

80.,3

C+D

3.,13

79.,6

165.,9 100.,8 163..0 114,.6 140.. 4 121,.7 150..8 123..2 129. 6 119..2 11

44.,2 189..7 128.,5 110,.2

43.,7 189..7 128.,1 109,.7 165..7 100..9 163.. 1 114,.6 140..2 113,.2 157..6 115..5 129. 5 116..8 11

79.,1

166..1 101..0 164.. 1 115,.0 127..6 155..9 110.,6 129..4 120. 9 126..4 11

166..0 100..8 163..2 114,.6 130..6 147..6 122.,9 129.,5 127. 1 126.. 4 11

128 .1 109 .7 165..7 100..9 163.,7 114,.6 125., 4 154..2 115.,6 129.,1 119. 1 126..5 11

93..8 162,.4 102,.8 138..0 125..8 128.,5 128.,5 128. 5 125.,8 17

93,.5 162,.2 104,.6 139..2 126..4 128.,5 128.,3 128. 5 126..4 16

94..8 162..7 103,.0 138., 4 126..1 128.,8 128.,8 128. 8 126.,1 18

164,.4

95,. 1 162,.7 101..9 138..0 126..5 128.,5 128.,5 128. 5 126..5 15

. 126., 5 128. 8 126..7 14

118,.2 161,.2 120,.8 139..0 126..7 128 ,8
165,.8 100..7 163,.2 114,.6 138..6 125..9 128.,5 128..5 128. 5 125..9 11

167..6

43.,1 190..0 128.,6 110,.3

42..6 190,.3

C--2'

79.,3

74..9

C--1'

3.,12

C+D

C+D

3.,9

3.,11

75.. 1 43.,4 191..4 128.,8 110,.1

C+D

3..8

3.,10

75.,1

C+D

3..7

C--10

161,.3 120,.8 138..6 125..9 128..6 128.,6 128. 6 125..9

C--9

95 .7 167..3

94 .8

43.,4 195,.6 164..1

43..1 197,.3 163..8

3..6

78,.9

3..5

95 .8

117,.9

C--8

136,.0 118,.0 161,.4 120,.9 138..7 126..1 128.,7 128..6 128. 7 126..1 12,13

96 . 1 166,.6

45,.0 187,. 4 164..1

42,.2 195,.8 163..6

110 .0

78,.1

79..2

C--7

121 . 7 136,.5

78,.4

190,.0 128,.5

44,.1

43,.8 191..7 128,.8

79,.7

3,.2

c--6

126,.9 121 .4 135,.9

C--5

191.. 7 126,.9 121 .5

191..6

C--4

3,.3

79,.1

3,. 1

44,.5

44,.6

C--3

3,. 4

79,.5

79 .5

3,.1

C--2

3,.1

Str .Mo. Solv.

Carbon-13 NMR chemical shifts of flavanones'

TABLE 3.1

100

101
R

(3.1)

R =R2=R3=H

(3.2)
(3.3)
(3.4)
(3.5)
(3.6)

R ' = R = H , R =OMe
3
2
R'=R =OH,R =H, pinocembrin
2
3
alpinetin
R'=0Me,R =H,R =0H
2
3
R'=OH,R =H,R =OMe
2
3
R = O H , R = H , R = 0 C H 2 C H = C ( M e ) 2

( 3 . 1 7 )

R'=OH,R =Me,R =OMe

3

( 3 . 1 6 )

( 3 . 1 0 )
( 3 . 1 1 )
( 3 . 1 2 )
( 3 . 1 3 )

strobopinin
R'=R =0H,R =Me
2
3
( 3 . 1 9 ) R * = O M3e , R = M 2e , R = O H , c o m p t o n i n
( 3 . 2 0 )
R'=R =0H,R =0Me
dihydrooroxylin
( 3 . 1 8 )

(3.7)
(3.8)
(3.9)

( 3 . 1 4 )
( 3 . 1 5 )

(3.24)
(3.25)

R'=0H,R =R =H
2
3
R'=OAc,R =R =H
2
3
R'=OMe,R =R =H
3
2
R' = R = H , R = O H
3
2
R'=R =H,R =OAc
3
2
R'=R =H,R =OMe
2
3
R'=R =H,R =OH
7-methyl linuiritisonin
2
3
R'=R =H,R =OAc
2
3
R'=R =H,R =OMe
liquiritigenin dimethyl

ether

purpurin
( 3 . 2 1 )

( 3 . 2 3 )

R ' = H , R = 0 - C H ( M e ) 2 linderatone
2
R'=Me,R =0-CH(Me)2
2
R'=H,R =<-CH(M8)2
isolinderatone

R'=0H,R =H
2

isochamanetin

( 3 . 2 2 )

R'=H,R =OH

( 3 . 2 6 )

R =R =H,R =Me cryptostrobin

3
2
R' =R = Me,R =H
2
3
R ' = H , R = R =Me
2
3
R ' = H , R = C H 2C H = C ( M e ) 2, R = M e
2
3
R'=R =R =OMe

( 3 . 2 7 )
( 3 . 2 8 )
( 3 . 2 9 )
( 3 . 3 0 )

41,.9 196.1

77,.9

162,.7

161 .1

156,.2

163,.3

43..5 196.1

43..6 195.8

45.,6 189.2

43..4 197.2

78..7

79..4

42. 6

42. 7 196.4

77.,6

74.0

77. 5

79.,0

3.32

3.33

3.34

3.35

3.36

43.6

197.2

192.0

163..5

164,.7

43. 7 197.3

196.1

41. 9

43.,6 196.2

80.,1

77. 8

79.,4

C+A

3.36

3.37

3.37

164..5

165..0

163..6

42. 0

79.,2

78.,4

196.2

111 .8

95 .4

95 .9

167,.4 113 .3

163,.3

165,.0

164.9

94 .9

98 .7

C-8

166,.2 105 .1
159 .1

161,.4 104 .7 162 .2

159 .5

162 .1

162 .2

161 .7

160 .8

162 .1

157 .5

163 .0

C-9

95,.1

165 .1
. 108,.9

95..9 166..8

96..5

C-3'

25

24

18
27
25

103..4 140.,0 127,.1 129.4 129..1 129..4 127 .1

28
25
29

128 .3 128,.3 126 .2

158..7 116..1 128
129..5 119..2 127 .1

104..9 139.,4 125,.8 127.9

103.,1 130.,7 128,.9 116.1

102..8 138..4 126,.2 128.9

128..9 128..9 126 .2

20

128.,6 128..9 126 .0

106..3 138..9 125,.9 128.7 128..4 128..7 125 .9

103..1 139..3 126,.0 128.9

20
23

26

128..2 128,.5 126 .2

127..1 129,.1 129 .2

103..4 139..7 126,.2 128.7 128..2 128..7 126 .2

101.,7 139..0 126,.2 128.5

130..5 140..2 129 .2 129.1

103..6 140..1 127 .3 129. 5 126..5 129,.5 127 . 3 26

103,.0 139..9 127 .1 129. 2 126..2 129 .2

, 127 . 1 26,15

31
35

159..4 113,.5 128 .6

160..3 114,.5 128.1

101.,7 130.. 5 128,.6 113.5

103..0 131..0 128 .1 114.5
163 .6
96 .0

101.,8 12 8.
,9 128,.2 115.2

94,.9 162,.7

102.,4 130.,0 128,.3 115.4 157..8 115..4 128 .3

97..1 166..7

168..0

95,.0 162,.9

95 .8
. 166,,6

97.0

95.,9 166.,7

33,34

14
30

96,. 1 164,.5

30

159..3 113,.1 127 .4

102.,3 129.,4 128.7 115.7 158.,1 115.,7 128 .7

126.,2 131.,0 127,.4 113.1

31,32

163,.6

163,.3

129..1 129,.3 127 .0

128.,1 128,.2 126 .2

22,23

C-6' Ref.

128..4 128,.6 126 .5

C-5'

103,.1 140.3 129 .4 130 .3 130..3 130 .3

, 129 . 4 25

103,.0 139..9 127 .0 129.3

101,.7 138..5 126 .2 128.2

C-4'

157..8 115..2 128 .2

95,.2

95,.5

C-2'

103.,1 130.,7 128,.8 116.2 158..5 116..2 128 .8

96.,2 116.,5

96..4 166.,9

C-l'

107,.8 139,.3 126 .5 128.6

C-10

163,.4 101.,8 124.,9 154,.4 115.6

161,.2

93..2 160..1 106,.4 161 .7

161 .1

158,.7 131 .0 157,.8

96..8 164..8 107.2

89,.5

91,.8 165,.3 106 .4 160 .6

92,.5

92,.9

95,.2 164,.6 102 .6

96,.8 163,. 1 110 .7

92,.1

95,.8

110 .1

108 .2

159 .3

161 .7

C-7

140,.4 125..3 145.,1 115,.6 162,.6

163,.7

196.4

163,.7

163,.3

3.36

44. 8

41.,1 196.5

162,.2

3.36

79.,7

79..9

3.31

44.,7 187.6

79..0

3.29

3.30

159,.7

3.28

187.9

44.9

77..8

3.26

160 .9

162 .6

165 .6

43..8 197.5

3.27

80,.1

43,.8 197.4

79,.9

162 .0

165 .6

162 .1

43,.4 197.0

3.24

112 .3

C-6

154 .8 129 .0

159 .6

C-5

43,.7 196.7

3.25

79,.7

80,.0

43,.6 196.7

79,.7

42,.0 196.1

45,.1 187.9

C-4

3.21

78,.2

78,.1

C-3

3.22

3.20

C-2

3.23

3.19

Str.No. Solv.

102

OR

OR*
3

(3.31)
(3.32)
(3.33)

R'=R =H,R =OHchamanetin

2
3
R'=Me,R =0H,R =H
2
3
R'=R =H,R =OH

(3.35)
(3.36)
(3.37)
(3.39)
(3.40)
(3.41)
(3.74)
(3.75)
(3.76)
(3.77)
(3.78)

R
R
R
R
R
R
R
R
R
R
R

(3.34) R ' = R = R = H , R = 0 H
2
3
(3.62) R ' = R = H , R = R = 0 M e ,
2
3
( 3 . 6 4 ) R ' = M 8 , R = R = 0 M e . R =H
2
3
( 3 . 7 9 ) R ' = M e , R = H , R = R =OH
2
d
4
(3.91) R ' = R = M e , R = R = H
dimethylstrnbopinin

=R =Me,R =H,R*=OMe
2
4
3
= R = R = 0 H , R =H, naringenin
2
3
=R =0H,R =H,R*=0Me, angophorol
1
2
3
R

=R*=OMe,R =OH,R =H
3
2
3
=OH,R =R* =OMe,R =H
(3.42) R ' = R 2 = H , R = O H , i s o b a v a c h i n
1
2
3
2
3
R
=
O
H
,
R
=
R
=H, glabranin
=R =R* =OMe, R = H
(3.43)
3
2
2
3
4
=R =R =R =0H, eriodictyol
(3.59) R ' = R = O H , R = C H 2C H = C ( M e ) 2
2
=R =R3=0H, R*=0Me, hesperetin
2
3
=R =R* =OH,R =OMe, h o m o e r i o d i c t y o l
2
= R 3 = R * = 0H , R = O M e
3
2
4
=R =0H,R =R =0Me

R 0

( 3 . 4 4 ) R ' = R 2 = R3 = H
3
2
( 3 . 4 5 ) R ' = R = H ,2R =3M e
R
'
=
M
e
,
R
=
R
=H
(3.46)
2
3
( 3 . 8 2 ) R ' = R = H2 , R = O H3
(3.83) R ' = H , R 2= M e , R3= O H
(3.84) R ' = H , R = M e , R = O M e

(3.47) R ' = M e , R = H
2
(3.48) R = H , R = H dichamanetin
2
(3.52) R ' = H , R = 0 - h y d r o x y b e n z y l ,
uvarinol

43..7 197..3 165..6 111..4

44..8 188..5 160..2 112..0 159.,0 108..2

79..0

78..8

79..0

79.,3

79.,2

77,,8

77.8

79.9

79.,4

79.,9

78.,3

3. 42

3. 43

3.44

3.45

3.46

3.47

3.48

3.49

3.50

3.51

3.52

79.,0

78.,6

78.,8

3.59

3.60

162..4 106.,1 131.,0 127..7 114..2 160.,0 114.,2 127,.7 36

97..0

38

43.,1 195..6 159..3 108..1 158.,8 102,.5

25

156.. 1 102.,3 138., 4 125..6 128.. 4 128.. 4 128..4 125 .6 45

162.,6 107,.7 159..6 103.,4 140.,1

150..2 111..6 137.,9 125..9 128,.8 128..6 128..8 125,.9 44

45.,9 189..6 152..5 138..7 153.,4 141..1

43.,6 197..6 160,.5 108..5

161..8 110.,3 135.,5 126..2 128..9 129..4 128..9 126,.2 42

143.,6 177,.5

42.,9 187..3 178..3 145.,7

42

147..6 104.,3 138.,9 126..9 128..8 128..8 128..8 126,.9

103.,4 139.,9 127..1 129..4 129..4 129..4 127,.1 25

158..3 108.,4 139.,3 126 .0 128..4 128. 1 128.,7 126,.4 28

157..0 107,,5 139.,5 126.,0 128..5 128., 1 128..5 126,.0 39

162.,4 107,.7 159..5

160.,3 110..5

160..0 102,.9

158..3 104.0 140.,5 126..6 129..2 128.,8 129..6 126,.6 39,40

159.,5 109..7 157..9 105.,2 139., 1 125. 9 128..6 128..4 128..6 125,.9 39,41

162..0 106,.0 164..0 103.,0 135.,0 128,.0 128..0 126..0 128.,0 128.0

43,,1 198..2 145..6 134..0 151.,0 130..9

43.,5 197..5 160..6 108..6

44.,7 188..3 160..0 114..6

162..4 103..0

43..0 196,.0 160,,0

43..5 196,.9

77.,8

95..8 170.,4

109,.0

43.,1 196.,4 156..6 103 ..6

131..2 112..7 145,. 4 149..8

47,47a

117 .9 47,47a

157.,7 105,. 1 156..0 103..5 129..0 127,.6 115,.5 160,.6 115,.5 127 .6 48

159..3 102..9 130..8 127,.7 115,.6 162,.5 115,.6 127 .7 48

151.,4 113..4 132.,0 106..9 148,.6 148..0 108,.6 120 .3 46

96,.6 162.,3

100..5

43.,1 196..8 156..2 107..4 157.,9 106,.6

44.5

42.,1 194..1 163.4

162.,9 106,.2 158.. 0 102..2 138.,7 126..6 128,.3 128..3 128..3 126 .6 21

93,.2

44.,3 190..8 107.,6

3.57

162..9 103..2 130.,6 127..7 114..3 160., 1 114..3 127,.7 36

94,.4 163,.3 103..3 130.,8 128..0 114.4 160.,2 114.. 4 128,.0 34

94,.2

40.,5 197.,2 159..2 103..9

3.58

33

C-6' Ref.

80.,2

C+D

C-5'

82.,0

3.56

C-4'

156.,9 107,.1 160..6 108.3 138..6 125..6 128,.4 129..3 128..2 125 .6 45

3.55

C-3'

44.,9 189..1 143..8 114..9

3.54

C-2'

78.,8

3.53

82.,0

78.,8

168..3

93.,7 166..0

95..2

C-l'

43..0 191..0 125..4 113..8 162.,1 109,.8 160..8 115., 1 129.,8 128..2 115..3 157.,7 115.,3 128,.2 37

45..5 189,.2 165,.1

43..2 196,.5 164,.0

C-10

164..3 103.,8 130.7 128..9 116..3 158.,7 116.,3 128.9

C-9

93,.7 163..0 105..1 131.,1 127..9 114.,3 160.,1 114..3 127,.9 33

3. 41

79..2

168..0

165..4

95..1

96,.6

3. 40

43..2 196,.0 164,.2

165,.5

79..0

45,.4 190,,9

78..8

95,.0

C-8

95..7 169..1

C-7

3.39

164,.9

C-6

3.,40

43..8 197,.9

C-5

80..2

C-4

C-3

C-2

3.,38

Str.No. Solv.

104

105

( 3 . 4 9 ) R ' = R = O H , R = M e , R =R = H
didymocarpin-A
. ^
3
2
( 3 . 5 1 ) R ' = R = O M e , R = M e , R =R =H
kanakugin
.
2
( 3 . 5 6 ) R = R * = H , R = M e , R > R = O C H 20
2
3
( 3 . 6 8 ) R ' = R = O H , R = R = R =H

(3.50)

dehydrodidymocarpin

Me

(3.53)
(3.54)
(3.65)
(3.66)
(3.67)
(3.81)

R ' = O H FR = R = R ' = H mundulin

2
3
R ' = O A c , R = R = P =H
3
2
R ' = R = 0 H , R = R 4 = H minimiflorin
2
4
3
R ' = R = R = O H , R = H orotinin
2
4
3
R'=OMe,R =R =OH,R =H
2
4
3
R'=OH,R =R =H,R =OH
lupinifolin

(3.55)

melanervin

(3.57) R=H
(3.58)

(3.60)

lonchocarpol

OH

R=Ac

(3.61)

lonchocarpol

78,.9

78..4

78.,3

78.,8

78.5

3 .61

3 .62

3,.63

3,.64

3,.65

3,.66

3,.67

3..68

3,.69

3..70

78.,2

78.,3

3.,73

3.,73

3.,74

41,.1 196.6

41.,8 189.2

43.,8 194.5

78.4

71.,3

80. 4

78. 0

C+D

C+D

3,,76

3.,77

3.,78

3.79

3.80

3.81

79. 2

78.,7

78.,6

42.,3 196.3

42.,1 196.9

43.,0 196.2

42,,1 196.3

42.,8 195.5

42.,1 196.2

42.,2 196.0

3.,75

78.,5

42.,2 196.2

42..0 196.6

44..1 197.9

45.,4 189.2

43..6 197.0

43..3 196.2

42..0 197.1

42,.1 196.8

43,.6 191.1

41,.2 196.6

41,.9 196.4

43,.8 188.1

42,.7 197.7

3.,74

78.,4

C-4

C-5

160,.1 128.7
157,.3 129.3

165..3 108.0

164.,2

95.7

166.,7

92,.9

161.,1

94,.7 167.,5

94,.8 167.,8

95,.8 166.,6

96,.4 166.,9

96,.2 166.,9

95,.9

95,.7 166.,6

95.5

93.8

94.0

95.0

95.4

95.4

95.1

94.8

95,.3 164.,4 107.0

165.,4 108.9

155. 6

108,.1 158.,8 102.2

119. 7 111..1 153.,2 133.8

165. 4

163.2

163. 9

163. 5

164. 0

163. 8

163.6

163. 4

161.2

163.2

96,,9

121,.8 154,,9 110.0

159.,6 115,.2 156,,6 102.1

161.,4 107,.1

149.3

157.6

157.0

157.0

159.8

156.7

161.8

154.7

156.3

C-9

159.4

152.0

162.4

162.8

163.0

162.9

162.9

163.0

162.9

162.8

159.8

161.7

160.8

161.3

161.2

95,. 4 164..7 107. 1 160.1

95.1

155..4 109.0

159..8 102.6

15 5.
,0 129,.0 159.,4

155.,8 109 .1

161.,6

C-8

171,.1 112.2

C-7

108 .9 158..8 103.4

93.5

96 .6

96 .0

112 .2

C-6

158.,2 109,.3

156.8

157.,0

163.,1

158..8

43,.2 195.6 171. 1

C-3

3.,75

80.,3

78.,9

3,,71

3.,72

76..2

75,.9

76,.8

73,.8

75,.5

74,.0

C-2

Str.No. Solv.

C-l'

C-2'

C-3'

C-4'

C-5'

101..8 126.6 156.4 111..4 129..9 120.7 126.8

51,52

50

49

50

129.,5 128..3 115..4 157.9 115.4 128.3

127.3

53,54

53,54

55

55

117.7 11

118.0 31,58

118.1 57

119.5 59
111..1 131.,5 115.. 2 145..9 145..6 116.5

101..8 129.,8 127..1 115..0 155,.8 115.0 127.1 45

157.4 123
104.,4 110,,7 157..4 106..9 129..8 106.9

102,,7 131.,1 114.,1 146.,5 148..0 112.0 117.7 58

103,.0 129.,7 113.,9 145..2 145..6 115.6

101,,8 129.,4 111.,1 147..5 146.,9 115.2 119.6 31

102,,2 131.,3 113.,6 146..6 147.,9 111.5

102,,1 131.,4 114.,3 146..7 148.,1 112.1

102,,0 129.,7 114.,5 145..3 145..7 115.6 117.9 56,32

101,.7 129 ,4
. 114.,2 145..1 145..6 115.3 117.8 31,63

101,.8 129.,3 127..3 115.,1 157..6 115.1

103,,9 131,,6 129.,3 116.6 159.,1 116.6 129.3

127.3

106,,1 135.,6 127.,2 122..0 151..0 122.0 127.2

112,,1 136.,1 127.,3 122..1 151..1 122.1

55

37,54

115..2 157..9 115.2 127.9 24

103.,0 130.7 127..9 115..7 156..2 115.7 127.9

102,.0 129.,0 127.9

109,.5 110.,5 154..7 108..6 130..7 108.6 154.7 52

154.7 52

153..7 116.9 129..9 120.9 126.9

103,,9 110.,5 154.,7 108..9 130.1 108.9

103..4 124.5

104..8 127,,1 156..2 111..3 129..7 120.7 126.5

103.3 126,,8 154..7 116..3 130..0 120.7 127.4

48

C-6' Ref.

104.2 130..8 127..8 115..7 160,,7 115.7 127.8

C-10

106

107

(3.63) Kushenol A

(3.69) R ' = H sophoraflavanone

(3.95) R ' = C H 2C H = C ( M e ) 2 e u c h r e s t a flavanone A

(3.73)

(3.70)
(3.71)
(3.72)
(3.90)

R = C H 2C H = C ( M e ) C H 2C H 2C H = C ( M e ) 2
sophoraflavanone A

R ' = R = R = H bonannione A
!
3
2
R =R =H,R =Ac
2
3
R'=R =Ac,R =H
2
3
R'=R =H,R =OH
nymphaeol A

(3.86)
(3.87)
(3.88)
(3.89)
(3.85) kushenol

R ' + R = O C H 20
2
R'=OMe,R =OH
2
R'=OH,R =OMe
2
R'=R =OMe

42,.8 197.5

190.6

75 . 4

74.2

73,.3

79,.4

3,.83

3,.84

3,.85

3,.86

42..6 198.5

77,.0

76,.9

75,.3

76..0

3..94

3..95

3..96

3..97

3..98

80..2

79..8

79..4

3.,103

3.,104

3.,105

46.,2 187.7

46.,3 188.1

46..4 188.0

42..9 198.2

39.,5 196.0

75..4

77..2

43..1 198.4

43..3 197.0

43..1 197.0

42..1 197.1

39..3 198.1

38..9 198.5

42..8 196.9

44.,9 187.9

3.,101

75..5

71,.5

77,.8

43,.4 196.5

45,.3 189.6

3.,102

78,.5

71,.4

3..92

3..93

3.,99

79,.2

3.91

3.,100

42..9 197.3

7 9 '.3

79,.5

3,.90

189.2

191.2

45,.2

3,.89

45,.5

79,.7

3,.88

79,.2

C+M

3,.87

45,.6

42,.9 198.1

42,.8 199.1

42,.7 197.8

75 . 4

C-4

3 .32

C-3

C-2

Str.No. Solv.

96,.6

95,.5

92,.0

129,.5

107 .7

92..9

108 6.

134 .0

133 .8

134 .7

134 .7

108 .4

111 .2

97,.6

167,.6

165,.6

165,.6

165,.7

162,.5

94,.5

94,.5

94,.6

95,.9

159,.3 108,.6

160,.0 108,.5

97,.2

165,.4

161 .8 108,.7

164 .8

161,.6

159 .2

159 .3

162 .3

159,.7

161 .7

154.0

154.0

155 .5

155 .3

162 .3

159 .5

C-7

C-9

C-10

C-l'

C-2'

C-3'

C-4'

C-5'

C-6' Ref.

102,.9 117..6 159..3 103.,6 156,.2 107..9 128..7

105,.2 127.,9 156..0 110..6 129,.3 121..0 126..3

108.5

91..9

102,.8 129..4 127,.3 143..7 145 .4 113..2 118..2 63

96.,2 164.,8 103,.1 119..4 155,.2 105..5 155 .4 115..7 128..9 66,70
96.,4 165.,0 103, 3 120..8 154,.1 103..7 156 6 117..3 128..8 67

95.,0 161..8 102 .7 129,.5 127,.1 143..6 145 .1 113..2 118..1 63,70

95..6 164.2

166.,7

166.,6

166.,7

166.,7

93.,6 163.,2 106,.7 136.,0 107..8 151..3 137 .3 154,.2 103,.0 69

93.,8 163.,3 106,.7 135.,9 113..9 145..3 142 .1 154,.7 109..5 69

120,.9 68
133 .7 154,.6 105,.0 69

101,.9 129.,6 118.4 141..9 145 .8

93.,7 163.,3 106,.8 135 .9

. 105..0 154.6

95.,0 163..5

162.,6 107.,6 160.,2 103,.6 111..8 156..1 103..6 159 .4 107..9 128,.6 49
162.,4 108.,0 160.,2 103,.3 117..9 159..3 103..7 156 .2 107..9 128,.6 61

167..8

168.,6

164..4

167..0

164..8 107..2 160..0 102 .1 129..5 128..1 127..7 155 .5 114..9 125..3 65,54

102..6 159..6

50
102 .2 111..5 157,.3 109..1 130 .5 102..8 159..4 50

154..4 102 .4 111..2 157..2 108..9 130.5

95..8 160.,4 102 .0 128..3 128..3 128.,2 155,.4 115..0 125..3 64

160,.9 129..0 154..6

160..6

164.3

95..0 161..3 102 .5 130..9 114..2 145.,4 145,.8 115..7 118..6 63

161,.4 104.,7 162. 2 103.,4 139..7 126..2 128.,7 128,.2 128.,7 126..2 22
164..7

62

62

62

61

40

131..3 109..7 149.,4 146,.1 111..3 118..8 62

96..2 154.0

108,.7 130.,6 110..0 147.,8 146,.8 115..4 119..6

157..0

155..5

96..3 154..0 108,.5 131..8 112..6 146.,0 146,.9 110..8 118..0

96.6

96..5 155..3 108,.6 132..8 108..5 148.,2 146,.6 106..9 120..2

95..1 162..9

158..5

157..1

157,.6

157..3

165..1

165..4 109.6

40

103..2 159..0 104,.3 127.,0 154..8 116..4 129,.9 120.,7 127..3 40,60

C-8

166..1 110..1 159..2 105,.6 126..6 154..8 116.,4 130,.0 120.7 127.3

103 . 4 163.0

C-6

160 . 1 111 .3

160 .2

C-5

108

109

(3.92)

Flemiflavanone

(3.96)

R=H nymphaeol

(3.97)

R = C H 2C H = C ( M e ) ,

(3.99)

Kuwanon

(3.93) R ' = O M e , R =H
2
(3.94) R ' = H , R =OMe

(3.98)

Kuwanon D

3.110

3.111

3.112

3.121

3.122

3.123

3.124

3.125

75. 8

104.4

102. 1

102. 6

101. 2

68 4

101 7

102 4

3.28 55.8;

3.44 60.6;

55.5;

55.8;

186 0

96 8

96 7

183. 5

188. 8

189. 5

186. 6

198.2

3.13 56. 0;

3.45 60.4;

96. 9

108.6

96.4

C- 3'
-

C- 4'

C-5'

98 7
161 9

C-

127 .7 155 5 114.9

73,54

125 3 54,65

101 .7 117 .6 153.5

112 .8 155 5 102.9

99.5

158. 7

109 7 161.2

159. 4

161. 2

100. 7 121. 0 125.8 109 9 161. 3

98. 7 119. 8 124.2 108 6 159. 7

99.5

98.3

80

159. 7 82

3 38 56. 1;
3.51 61. 5, 61. 6;

3 .37 55. 0;
3 50 61. 1, 61. 4;

3 37 55. 6;

3.56 56 .4;

3.27
3.56 56 .4;

3.57

3.40 54.4,

3.20 59 .7 ;

3.10 55 .5;
3.39 55.5, 55.9;

3 .19 60 .5;

3._9 55 .4, 55 .7;

3 .17 55.8 ;

3 .8 55. 6;

3.15 55.1, 55 .4;

3 .7 55 6;

3.11

76,79

79

78

76,77

75

75

72,74

159. 6 81

105. 6 121. 7 150.2 117 V 129. 3 121.4 125. 5

98.2

99.5

115 0 153. 0 105.8 156. 6

109.4 160. 2

110 .0 154. 3 108.4 128. 4

98 7 119. 5 124.7 106 6 159.9

99 9 122. 2 125.6

101 1 126. 4 124.5

101 1 121 1 124.9

103 2 118 3 151.9

103 1 118 6 151.6 110 .0 154 3 108.6 129 5

130 7

127 7 73

103 .8 118 .7 154.0 108 .4 154.0 107.2 130 6 72

102 .1 129 .5 128.1

101 .8 118 .1 153.2 102 .3 155 5 115.5 127.3

101 .6 117 .3 153.4 103 .1 155 5 125.2 121 6 71

45

60

Ref.

102 6 164 4 100. 8 121. 0 125.6 110 0 161. 5 99.6 161.2 82

97. 5 162. 4 110.0 121. 5 125.0 108. 2 161. 4 101.2 157.3 82
96. 0 164. 5 103. 1 119. 1 155.2 111. 1 150.9 109.3 129.2 82

55.7;

3.49 60.8, 61 .1;

162 .0

159 .6

94 .2 160 7

53 .0

3.5 55 .4;

167. 4

165. 5
162. 4

164 .8
164 .8

94 .4 160 .0

96 .5

C-2'

C- 1'

107 .1 135 .8 126.6 121 .3 150.1 121.3 126.6

.5

- 10

165 .4 103 3 118 4 153.0 109 .7 153 3 107.5

160 .1

165 .3

160 .0

160 .2

160 .7

96 .45 164 .3

95 .8

95 .9

96 .3

161. 1 109 2

164.3

3.35 55 .0;

3.14

3.4 55.7;

165.3

160. 7

97. 6

197 7 103. 2

157. 5

167. 3

167. 6

164 2

162 4

167 4

167 5

53 0 211. 4

160 7 109. 7

183 7

187. 1 162 8 108 6

109 0

162 1 102 9

3.30 56.1, 61.1;

55 1, 55.4;

3.12

55.5;

165 .3

165 .3

168 2

164 .3 106 .9

96.6

95 .3

161

165 .6

96 .0

167 .7

96 .8

164 .8 108 .2

164 .3 108 .4

~>

96 .3

95 .1

94 .5

108 .9

160.0

164.3

156.7

C- 9
157 .5

C- 8

162 .3 102 .5

C- 7

165 .0

161 .5

161 .2

161 .6 107 .6

143 .8 114.9

188. 4 163 9

42.4 197.4

91.2

92.5

92.0

90.8

39.2

90.6

92.0

C- 6

158 .4 103 .2

C- 5

186 4 158 7 102 8

197 5

197 5

198 5

196 9

197 6

197 1

197.1

Other Signals: OMe : 3.2 55.5;

3.120

3.119

3.118

90.5

90.5

101 .0

3.116

3.117

99 3

42.7

42.8

42.6

41.2

43.2

42.1

41.6

74 .9

74 .9

76 .6

73 .6

75 .3

188 6

C- 4

41.4 196 7

44.9

C-3

3.115

3.114

74 .1

3.109

3.113

73 .6

78 .5

78.1

3.108

3.107

3.106

Str.No. Solv . C-2

110

Ill

(3.100)

Kushenol

(3.101)

Kushe-nol

(3.103) R ' = M e
(3.104) R ' = H
(3.105) R ' = A c

(3.102)

(3.106)

methoxymatteucin

(3.109)

R = C H 2C H = C ( M e ) 2
Euchrestaflavanone

(3.108) R ' = C H 2C H = C ( M e ) 2, R 2 = H
c u d r a f l a2 v a n o n e
(3.112) R ' = H , R = C H 2C H = C ( M e ) 2

(3.110)

R = C H 2C H = C ( M e ) 2
Euchrestaflavanone A

56.2,

3.45

8.1,

6.8;

3.18

8.7 ;

7.0;

3.55

3.16

7.5,
80.4,

127.7.

127.5,

116.1,

115.5,

3.67

28.4x2;

3.116

18.1;

3.53

79.1,

28.5x2;

77.8,

128.1,

3.121

17.6;

128.6,

115.0,

25.9,

136.9,

C H = C H C ( M e ) 2:

118.7,

25.4,

25.8,
21.3,

3.101

115.9,

28.3;

3.53

127.2,

17.4;

79.3,

121.6,

3.122

17.6,

125.2,
28.5,

32.2,

27.5,

17.9,

76.2,
28.4.

118.5,

123.5,

22.5,

27.8x2;

127.5,

-,

137.0,

130.6,

123.5,

3.69

3.65

3_._4 1 1 7 . 8 ,

3 .66

25.9,

25.5,

115.6,

18.2.

17.6;

77.0,

78.5,

32.1,

3.108

17.5;

25.5,

134.3,

115 .6 ,

130.6,

126.4;

42.4,

7.1,

169.. 2 ,

56. . 3 ,

27.9x2;

126 . 5 ,

3.116

17.9;

25.5,

131.7,

122.9,

156 . 2 ,

115.6,

23.5,

-,

3.44

3.105

56.1,

3.24

130.5,
25.8,

127.6,

132.2,

122.4,

28.4,

115 .6 ,

155.1,

122.9,

25.5,

3.57

127 . 1 ,

17.5;

28.4 ;

17.7;

28.5,

23.1,

133 . 1 ,

25.5,

17.7;

25.7,

78.3,

25.8,

3.31

3 .33

131.1,

25.6,

127.8,

121.3,

126.9,

25.5,

134.0,

127.7;

135.5,

3.79

3.89 56, . 0 ,

55.8;

21 . 3 ;

126.2;
30.3,

23 . 9 ,

23.5,

20.7,

20.6;

56.0,

61.1;

55.6,

3.104

56.2,

3.78

168.3,

3.35

3.54

60.2;

134.0,

16.7,

31.4,

8.4.

7.5;

20.7;

56.6,

56.0,

55.6;

3.88

3.77

3.28
7.9,

21.9,

23.6,

3.84

127.3;

132.6,

122.0,

29.9,

56.2,

169.5,

81.;

29.3,

120.5,

115.6,

116.9,

25.1,

130.1,

87.7;
16.7,

126.2.

122.9,

123.4,

3.27

3.16

56.1,

61.3;

55.9;

56.3,

3.75

8.6;

43.2,

131.1,

22.1,

3 .65
3.108

135.3,

122.8,

-,

156 . 2 ;

22.0,

21.8,

3.67

3.60

18.0;

18.2.

28.1x2;

117.2,

3.123

28.1,

77.5,

31.2,

3.109

17.8;

17.5;

26.0,

25.7,

17.8;

25.5,

25.7,

137.9,

139.0,

139.1,

23 .1 ,
21 . 9 ,

23.9,

115.9,

115.6,

155.0,

3.25

29.1 ,

134.0,

126.5;

42.4,

7 .5 ;

3 .83 8 . 0 ,

3.26

3.103

20 . 7 ;

62.4.

168.8,

27.5,

8.1 ;

7.9;

105.0,

31.4,

127.3,

127.5,

131 .1 ,

122.9,

118.6,

132.7,

-,

130.0,

122.0,

28.5,

22.0,

130.2,

122.8,

20.1,

123.4,

21.5,

3.66

21.8,

3.58

17.8;

3.22

3_^ 65.3,

3.42

17.7;

3.100

25.5,

C H 2C H = C ( M e ) 2:

O C H 2C H = C ( M e ) 2:

127.1.

- p - h y d r o x y - C H 2- C 6H 4:

120.5,

22.4,

-,

23.9,

23.6,

132.5,

16.7,

-,

31.5,

3.21

42.4,

23.6,

21.9,

35.7,

16.7,

29.1,

3.29

21.8,

- 0 - h y d r o x y - C H 2- C 6H 4:

29.3,

3.23

7.4,

3.19
3.82

52.4,

6.9;

8.7 ;

3.18

20.9x2.

3 .14

53.6, 55.6,

21.0;

3.124

56.2,

61.1;
3.87 5 6 . 1 ,

60.2;

60.8,

61.4;

3.68
56.3,

55.8,

60.4;
3.86
3.94

168,.9,

60.6;

- C H - C H ( C H ( M e ) 2) C H 2C H 2C ( M e ) = C H - :

- C H - C H O A c - C ( M e ) 20 - C H - 0 - :

3.17

7.9;

168.8,

3 .,107 1 6 8 . 6 ,

55.6,
60.0;

60.0;

3.11

56.6,

20.9;

C H 3:

20.5;

3.64

55.4,

56.2,

168.9,

3.8

3.,105 5 6 . 1 ,

O C O C H 3:

60.3;

55.7,

3.93

61. 5;

56.2,

3.84

60.4;

55.5;

55.7,

60.4;

3.62

3 .83

59.5;

112

113

(3.114) R=H Sanggenon

( 3 . 1 1 5 ) R = C H 2C H = C ( M e ) 2 S a n g g e n o n
OH

(3.111) R=H kuwanon

( 3 . 1 1 3 ) R = C H 2C H = C ( M e ) 2 k u w a n o n L

( 3 . 1 1 6 ) R ' = R = R = R =H S a n g g e n o n A
2
3
(3.117) R ' = R = R = H , R 4 - A c
2
3
( 3 . 1 2 2 ) R ' = R = R 4 = H , R = C H 2C H = C ( M e :
Sanggenon L
1
2
3
(3.124) R = R = R = M e , R = H

OH

( 3 . 1 2 3 ) R = C H 2C H = C ( M e ) 2

Saggenon

OH

OH
Saggenon C

(3.118)

6-

(3.119)

6 - * Saggenon D
OH

OH

(3.125) Saggenon

133.8,

26.2,

124.2,

131.9,

118.2,
25.8,

127.8,

39.6,

26.6,

25.8,

3.100

16.7,

25.7,

30.9,

-,

91.4,

27.4,

47.4,

149.1,

19.1,

111.1,

31.5,

3.63

72.1,

23.9,

124.6,

131.3,

27.8,
25.8,

47.8,

3.61

17.9.

115.7,

124.5,

27.0,

124.1,

26.3,

17.9;

31.8,

131 . 6 ,

91.5,

131.5,

25 . 7 ,

72.0,

3.73,

133.2,

121 . 4 ,

28.3,

17.7;

135.8,

117.8,

131.7,

21 . 2 ,

17.8;

27.1,

3.85

24.9.

131.2;

126.2,

37.5,

40.5,

25.6,

121.3,

3.125

124.4,

107.4,

38.9,

38.2,

16.2,

163.7,

3.112

23.4,

136.8,

133.7,

129.1.
27.1,

32.0,

24.1,

26.6,

130.9;

162.3,

107.0,

111 . 1 ,

72.3,

19.3,

87.7,

124.9,
107.5,

116.7,

156.0,

208.5,

102.5,

149.2,

23.9,

154.0,

37.5,

25 . 8 ,

111.1,

18 . 2 ,

2 5 . 6 , 17.7; 3.71 21.9,

131 . 5 ,

19.6,

132.1,

123.9,

39.6,

25.8,

16.2,

165.6,

3.111

103.8,

46.6,

165.6,

132.8,

117.9,

22.1;

131.3,

25.8,

27.6,

116.0,

108.4,

210.7,

157.4,

45.7,

103.1,

70.6,

C H 2C H ( C ( M e ) = C H 2) C H 2C H = C ( M e ) 2:

3.60

38.5,

134.3,

156.6,

108.4,

123.9,

156.8,

38.9,

132.0,

38.9,

103.2,

C H 2C H C ( M e ) 2O H :

3.121:

23.5,

156.8,

C H - C H = C ( M e ) C H 2C H ( 2 , 4 - d i h y d r o x y p h e n y l ) C H ( 2 , 4 - d i h y d r o x y b e n z o y l ) :

3.99

125.0,

149.3,

125.7,

123.8,132.0,

23.6,

135.9,

18.2;

120.9,

26.3,

27.9,
47.8,

26.4,

41 . 9 ,

28.3,

41 . 0 ,

16.2, 39.8,

23.1,

132.1,

20.6.

17.3.

25.7,

25.3,

17.6.

79.5,

25.5;

135.5,

139.3,

3.72

125.7,

17.6;

27.9,

78.6,

43.0,

68.1,

42.9,

41.0,

131.2,

16.7,

31.2,

28.5,

3.92

3.102

17.8.

C H 2C H O H C ( M e ) 2:

C H 2C H - C ( M e ) 2:

124.3,

135.5,

27.5,

124.2,

132.1,

22.7,

125.1,

3.73

25.6,

23.3,

16.1,

41.6,

17.5,

124.2,

3.7Q 21 . 1 , 121 . 4 ,

26.4,

130.6,

22.7,

C H 2C H = C ( M e ) C H 2C H 2C H = C ( M e ) 2:

78.7,

3.115

-,

125.0,

15.8,

3.73

128.0,

17.8.

)CH C H = C ( M e ) 2 :

C H = C H C ( M e ) C H 2C H 2C H = C ( M e ) 2:

25.8,

122.5,

CH C H ( C ( M e ) = C H

114

115
Similarly
and
shift
ppm

in d i - C - m e t h y l a t e d

difference

of

less

still

C-6 absorbs

(3.85)

C - 6 and

C-8 is

f i e l d than

exhibit

95.1

In
as

former

102.8 0 . 6

(3.53)

(3.81)

at

96.6

108.0

and

revealing

the

yranof lavanones
minimiflorin

C - 6 and
Both

(3.65),

C-6

and

C-8

Seligmann and

Wagner

have

C - 6 due

position

Hence t h i s

to t h e

than

i s not

the

family

[21].

The

an abnormal

of

the

proposed

structure for

as

Mitscher

ert

3.92

allyl

by
oxide

tant s i g n a l s a r e
commodated

as

due
per

moieties

aL

[64]

bonded

at

to e p o x y c a r b o n s
earlier

ppm,

kushenol

and

at

108.4

substitution

8-prenyl

orotinin

(3.66)

[51,52]

at 6 108.70.7

resonances
3.61

substituent

give

rise

to

[48].

flavanone,

C-8 resonance

of t h e

1,2-diaryl

methyl

substituent

melanervin

absorbs

at

ethyl

lower

substituent

at

C-6

position.

flemiflavanone-D has

been

recently

phenomenon.

The earlier
dimethyl

and

resonates

characterized

higher * -effect
oo-effect

0.1-0.2

[49,61].

C-8 resonances

in difuranoflavanone

triphenylmethane

(3.44)

chemical

at

lavandulyl

having

S 112.2

of

revised

A (3.63)

C - 6 in c a s e of later

[45],

[45],

at

kushenol

at

than

C-8

at

respectively.

a single absorption

(3.55)

and

(2",3"7,6)

mandulin

and

C-8 resonances
clearly

but

in

[40].

flavanones,

respectively

linear

lupinifolin

C-8 resonance

substituted

of

and

field

comparatively

the

C - 6 and

ppm

C-8 in case

such

demethoxymatteucinol

the

Lavandulyl

at

such as

(3.82),

lower

and

flavanones,

2'-hydroxydemethoxymatteucinol

proposed

h a v i n g V , ^ - d i m e t h y l a l l y l and
C - 6 and

at 6 4 2 . 9

structure

C-3

and
(see

positions.

43.0

The

w h i c h cannot

Chapter

1,

t j impor-

be

Section

ac-

1.4).

13
Based
none,

earlier

revised
cture

as

of

on

C shielding

described

as

data

the

s t r u c t u r e of a C - m e t h y l a t e d

5,7-dimethoxy-8-C-methyl-flavanone

5-hydroxy-7-methoxy-8-C-methyl-flavanone

prenylated

flavanone)

recently

flavanone

(3.91)

kuwanon

cally

the

as

is

located

at

108.4

i n foot n o t e s

and

his

coworkers

(3.111)

and

kuwanon

Diels-Alder adducts

at

C - 3 ' position

and

109.7

to Table

in

by

Maillard

[72]
L
of

both

respectively.
3.1,

has

been

The

stru-

(S^^'-trihydroxy-S'-methoxy-S'-prenylated

characterized

et^ i d

[47]

as 5 , 7 , 3 ' - t r i h y d r o x y - 4 ' - m e t h o x y - 5 ' - p r e n y l a t e d f l a v a n o n e

Nomura

[22]

[23].

flava-

isolated

3.113).
chalcone

cases,
The

novel

These
and

are

been

revised

[47a],

flavanone
regarded

flavanone.

therefore

additional

has

(3.57)

The

derivatives
biogenetisubstituent

C - 3 ' reesonance
13
C resonances

absorbs

are

given

116

novel

characterized
tuent
an
to

at

tions

by

C-3

epoxy
the

bridge

resonance
about
the

5-10

tuents

are

can

be

present

assigned

units.
ppm

formed

183.7

in

and
ppm

high

field

substitution

to

at

of

remain

almost

side

in

position
substituted

ortho

position,
suosti-

euchrestaflavanone
and

chain

its

C-3

and

represented

by

addition

of

C-6

providing

Sanggenon

at

21.3

C-8

which

and

the

C-9

modified

and

enolic

C-2'
at

nature.

site

C-3'

for

at

The

and

be

absorbs

(3.119)

position.
an

The

C-2 also

to

dehydro-

substitution

and

211.4

(3.118),

and

sanggenon

C-6

positions.

considered

chalcone

and

ring A

198.2

sanggenon
are

(3.118)

cyclohexene moiety

having

at 6 8 . 2

are

is

Diels-Alder

of t h e

C - 3 of

the

Due

additional

carbonyl
ppm

resonances

whereas

absorbs

at

epoxy

C-5

at

significantly

[80].
FLAVANONOLS

the

3-hydroxy

flavanone
C-2

leads

substituted

to

resonances

about

30.5

flavanones.
and

respectively

5.0

Hydroxyl

ppm

whereas

downfield

C-4

resonance

uninfluenced.
to

C - 2 and

the

existence

C-3 resonances

[29,37,45,55,59,61,83,96].
of

reveal-

methylene

chain

at S 2 7 . 5

These

positions appear

position

shifts

are

carbo-

hence
The

free

Therefore,

prenyl

The

21 w h e n o x y

(3.121).

The

between

Flavanonols

3.2)

one

[79,81].

(3.120)

C-6
due

category

3.3

tions,

has

absorp-

deshielded

side

around

resonances

of

sanggenon

by

in orientation

C-4

methylene

and

biogenitically

109.20.5

ring

prenyl

at

positions.

82].

via

results

their

compounds

relatively

substi-

This

and

81,

been

ring

position.

modification.

of

but

methylene

unique

(3.119)

Vafzelin

of

the

further
D

prenylflavanone

differ

to

6 27

ortho

two

at

prenyl

aromatic

[76-79,

these

has

[73].

sanggenon

at

both

exist

in

substituent

around

C-2

skeletal

methylene

prenyl

at

at

respectively

to

possess

with

C-3 resonances

resonates
the

the

in

there

positions

derived

If

absorbs

group

C - 2 and

due

to

These

cyclized

at 8 1 8 7 - 1 8 9 . 5

substituent

ring.

(3.109)

both

shielding

comparison

methylene

get

hydroxyl

of

dehydroprenylflavanones

coworkers.

also

and 9 0 . 5 - 9 2 . 5

ppm

in

aromatic

then

his

bear

nature

3-prenyl

flavanone,

and

(C-4) absorbs

10

ppm

of

which

and

at 9 9 . 3 - 1 0 2 . 4 ,

ing

to

Nomura

position

quaternary

nyl

of

category

methine

type.

Among

of

the

appear
Both
these,

oxygen

functions

between
of
C-2

70.9

these
is

at

C - 2 and

and

85.6

resonances

represented

posi-

ppm

(Table

and

C-3)

(C-2
by

C-3

the

downfield

117
signal

resonating

71.0-74.1

ppm,

The

chemical

C-2'

position

of

the

nates

C-3
at

usually
hence

shift
by

of

an

at

hydroxyl

C-2

exerts dependence

group.

flavanonols.

Hence,

ppm.

the

the

presence

of

the

tion

C - 2 resonance

of

C-2

the

at

get

a l s o upon

about

the

nance
absent

in

5 ppm

to

-effect
of

shifts

of

and

the

the

ppm

appear

respectively.
at

C-2

in

axial

and

Similar

resonance

be

used

for

upfield

substituent.
(1

or

shift

Esterificappm)

of

the

of

that

his

the

In
C-3

orientation

have

85.0,

2,3-trans
are
in

194.2

hydroxyl
thus

therefore,

shifts
of

group

at

Such

3-acetylated,
at

ppm

and

upfield

upfield

position

shift
as

3-acetylpadmatin

of

the

due

to

as

due

well

[45,55]. A compa(3.149)

3-OH group

but

Similar

3-OH group

with

causes

C-4 respectively
[90].

are
ab-

C-3 position

of

reso-

group

5-OH group

C-3 resonance

C - 5 owing

5-methoxylated

at

acetylation

92]

interactions

of

C - 2 and

91,

to a

carbonyl

significant

with

5-unsubstitu[59,

giving rise

In

12

In

ppm

upfield
without

observations

were

also

made

[91].

Carbon-13

(5.134)

3-OH group.
and

the

chelation

of t h e

by

exert

and

acetylation

coworkers

the

at

by

resonates

-effect)

dependence
substitution

the

not

[33,55,84,88,93],

89].

C-4

any

191

demonstrating

,4' -tetrahy droxyf lavanonol

C-4

reso-

e s p e c i a l l y upon the

interactions

ppm

chemical
(

induced

hydroxyflavanonol
and

NMR

chemical shift

shifts

shifted

[87,

loss

reveal

Recently,
1

C-2

C - 2 can

shift

does

of

a c y l a t i o n of h y d r o x y l

4.4

b y S c h i l l i n g and

5,7,3

of

C-4

however

flavanonols

hence

the
1

the

bond

198.7

ppm

effects

(3.146)

2.9

affecting
aoout

and

flavanonols,

the

padmatin

shifts

the

an 6 ' - o x y
upfield

between

downfield

ppm),

combined

for

derivatization

hydrogen

196.0

3,5-diacetylated
the

of

pattern

resonates

189.7-192.1

(184.8-185.9

of

C-2

2 -hydroxylated

substituent

of

etherification

in

at

shifts.

substitution

flavanonols,

substituent.

an

the

a c y l a t i o n or

ppm

shift

2'-oxy

causes

shift

5-methoxylated

at

rison

also

the

C-4

intramolecular
between

sorbs

2'-oxy

also expected

substitution

flavononols,

and
to

chemical

ring

C - 5 and

ted

75.5-79.2

chemical

the

upon

the

appears

chemical

(esterification -effect).

The
the

is

3-OH group

resonance

upon

of

upon

signal

their

2'-unsubstituted

3-4

predicting

and

at

2'-methoxylated

Thus,

C-3

distinguished by

In,

whereas

upfield

by

whereas

well

substituent

ppm

ppm

are

the

oxy

82.4-85.6

78.3-85.6

these

74.0

NMR
been
and

equitorially

shifts

and

reported
194.2

compound,

2,3-cis

chemical

(5.133)

[59]

and
aryl

oriented

compound.

for

the

2,3-cis,

,4 -tetra-

2,3-trans, 5,7,3
at
and

in

73.5

hydroxyl

whereas
The

which

82.7,
aryl

unusual

C-2,
and

C-3
191.4

substituents

substituent
preference

is
for

C-5

196,.0 163.6

C--4

78..3

3.,138

3..139

3.,140

168,.8

155,.6

93 .8

C-2'

C--4'
C--5'

85

59
84
55

113 .7 129.,4 116.2 145. 6 146 .4 116.,6 119..7

115. 0 157,.9 115.,0 129..5

73.,2 197.9

72.,9 190.,0 162.3

72..9 196.,3 164.4

83..1

84J

82..6

84..3

3.144

3. 145

3. 146

164.7

72.,9 184..9 143.9

71.,7 197.,1 163.3

80..6

3.,143

3. 144

71..5 197..4 163.2

72.,0 196.,3 155.8

82..7

82..7

3.,141

70..9 198.,4 163.7

74..1 185..9 160.6

94.9

95 .5

95.,4 169.,0

95.,6 164.,9

55
87

160..6 112 .3 133..2 128.8 122. 1 151 .7 122..1 128..8

100 .9 114.2 159.0 103. 0 157,.5 107.,1 130..3

45
89
59
90

164..0 101 .3 129 ,3

. 115. 6 145. 8 146 .5 115.,6 120..4

93,.4 162..8 102 .6 128.,5 115.3 145. 8 145,.0 115.,3 119.,4

94,.4 163..2 102 .2 129., 4 115.7 145. 5 146,.5 115.,5 120..3

29,85

128. 1 129,.5 128.,1 126.,9

100 .6 128.,1 115.3 144.9

145,.7 115.,3 119.,2

45

160..3 100 .0 136.,4 127.2 128. 2 128 .7 128.,2 127.,2

159..8 105 .9 135..3 126.9

88

162..3 100 .3 129..6 147.8 119. 1 146,.1 115.,0 111..6

163..3

95 . 1 162..5

97., 0 168., 1 95 .6

96.,1 166.,8

115.,5 157.,4 109 .6

108.,1 159.,1 102 .8

96.,0 166.,8

96.,5 167.1

123.,6 156.,0 108 .2

73..5 185..7 149.8

55
55

122..7 155.,6 110 . 1 160,.4 111 .0 132.,9 128.9

122. 1 151 .8 122.,1 128..9

98 .7 161..6 106 .1 128..0 129.4 114. 9 157.6 114.9

129..4

94 .5

116..4 162..8

160,.6 100 .3 127.,8 129.5

151,.6

162,.9

95 .4 162,.0 101 .6 129..4 130.3 116. 1 159 .0 116.1 130..3

105..7 162..3

111..7 153..4 133 .3

96 .0

85

95..9 169..1

59

85

162,.4 100 .7 125..8 129.2 115. 3 158 .2 115..3 129..2

115. 0 157.9

86

101 .4 127..5 129.6

115..0 129..5

162,.6

162,.4 101 .3 129..2 129.4 113. 6 159 .6 113..6 129..4

83
84

105 .3 131..3 127.4 129. 1 128 .6 129..1 127..4

83

C--6' Ref.

128. 6 129 .2 128..6 127,.6

C--3'

102 .2 126.,5 129.3 115. 9 158 .5 115.,9 129..3

95 .5

93 .9

C--

101 .9 129..4 130.4 116. 3 159 .2 116..3 130..4

96 .4 164,.6

93 .1

C--10

163,.0 100 .5 130..5 127.6

C--9

110..7 152..6 133 .4 151,.4 114 .0 128..7 115.4 145. 8 145 .3 115..9 119..1

96..6 167..4

95..0 167..7

94,.9 167.6

97,.5

136,.3 160..3

96 .0

C--8

107..9 164..7

3.,142

80..6

80..9

C--7

96,.9 167,.5

C--6

72..6 190..6 159.6

71..6 198..3 160.6

82..4

82,.9

194..2 121.2

73,.7 198..4 166.3

74.0

73,.5 191,.4 120.2

72,.9 192,.6 164.2

72,.0 191,.5 163.4

71,.7 198,.5 163.1

71,.6 198,.3 163.0

73,.7 198,.4 165.3

72 .8 191,.2 142.7

72 .5

C--3

84,.9

85,.0

3.,137

82,.7

81,.7

80,.2

83 .1

82 .7

85 .0

3.,136

3..134

3,.131

3..135

3,.130

3,.129

3..133

3 .127

3,.128

3,.132

83 .5

3 . 126

83 .5

C--2

Str. No. Solv.

Carbon-13 NMR chemical shifts of flavanonols

TABLE 3.2

118

119

R 0

(3.126) R ' = R = R = H , p i n o b a n k s i n
2
3
(3.128) R ' = R = H , R = 0 H a r o m a d e n d r i n
2
3
(3.129) R = R = H , R = O M e
2
3
(3.130) R ' = H , R = M e , R = O H
2
3
(3.131) R ' = A c , R = H , R = O H
2
3
(3.132) R ' = A c , R = M e , R = O H

(3.127)
(3.135)

R = M e , 2R + R = O3 C H42 0 , R =H
R=H,R =Me,R =R =OH 6-methyl
a r o m a d e n d r i n OH

HO

(3.133)

2,3 c i s

(3.134)

2,3 trans

(3.140)
(3.141)
(3.151)

R ' = 0 H , R = F = R * =H
2
3
R'=0H,R =R =H,R"-=0M6
2
3
4
R ' = R = R = H , R = C H 2C H = C ( M e ) 2
3-hydroxyglabrol

R 0

(3.136) R ' = R = R = H , b o n a n n i o l A
3
2
(3.137) R ' = R = H , R = M e , bonanniol
2
3
(3.138) R ' = R = R = A c
3
2
(3.139) R ' = R = A c , R = M e

OR'

2
(3.142) R ' = R = H * mundulinol
2
(3.143) R ' = A c , R = H
l
2
(3.154) R = H , R = O H , l u p i n i f o l i n o l
2
(3.155) R ' = A c , R = O A c

C+D

C+D

A+V7

A+W

A
D

3.,150

3.,151

3.,152

3 . ,153

3 . , 154

3 . ,155

3 . ,156

3 , ,157

3 . , 15 S

3 . .15*

3 . , 160

3 . .161

3 . , 162

3 . , 163

3 . . 164

3 . ,165

3 . ,166

3 . ,167

3 . , 168

3 . ,170

3 . , 16*

3,,149

C-4

73..0 192.2

73..4 193.2

73.,5 184.8

72.,7 191.9

72.,9 192.6

72.,5 189.7

C-3

84..5

75..5

79..0

79..2

81..1

81..9

90..1

82..4

83..2

78..6

78..5

78..6

78..5

83..4

84..3

79.,9

85..6

184.3

73,.2

197.9

73,.4 195.2

72,.7 198.7

72,.5 198.8

73,.9

73,.4 192.5

71,.0 194.9

72..0 189.3

71..6 197.5

73..4 189.7

72..9 192.0

73..5 189.6

73..1 192.1

72..9 190.8

73..1 197.7

72..9 184.7

72..0 195.7

82., 1 73..3 186.7

84.,3

84..4

81..1

81.,4

81.,7

83,,6

3 . ,147

3.,148

C-2

Str.No. Solv.

93. 6

95. 9

C-5'

91
91
45
45
89

162.,7 113.,3 130.8 104.7 153.,3 138. 8 153. 3 104.7

160.,5 100.,0 130.7 128.7 115.,4 156. 3 115. 4 128.7

109,.7 159.,6 105,,9 132.8 128.0 121.,2 150. 9 121.2 128.0

161.,3 101..0 129.7 115.6 145.,4 146.2 115. 5 120.6

95,.6

95,.1

108 .7

166,.7

108.,8 162 .6

93.,5 164.5

97.,2 165,.6

96.,4 166,.3

108 .1

93 .5

96.1

96 .2

92 .4

95 .9

163,.1 107 .9

163..8 109,.0

163.2

163..6 108,.8

165..2

165..2

157.4

159..2 102,.6

166..4 100,.9

96.,3 166 .3

95 .1

95 .1

161,.3 101,.0 128.9

162,.8 100,.5 123.9

37
89

107.8 146,.0 133,,9 146.,0 107.8

93
154.2 113,.8 153.,4 111.,2 128.1

159,.6 101,.4 115.7 157.6 103,.9 159.,4 107.9 130.0

159..7 101,.6 115.7 157.7 103.9

93

96

163..8 104.3 130.8 104.3 153,.0 138.,5 153.,0 104.3

159.3 107.,8 130.1

95

163..2 101,.4 127.1

163..1 105,.9 130.9

96

104.8 152,.0 137.,5 152.,0 104.8

111.3 147,.2 141.,0 147.,2 114.9

85,73
95

106.9 145..6 133.,4 145.,6 106.9

107.4 156,.1 133. 8 156.,3 107.4

161..0 102..8 132.9

163.,3 100..4 127.1

161..5 103..8 115.1

61
94

130.1

159.6 104..1 157. 9 107.9

161.,1 103..4 116.2

156.7 103..9 159. 1 107.4 130.6

93

156.8 104..0 159. 3 107..5 130.6

161.,5 104.0 115.2

89
61

110.1 149.,2 149. 7 111. 1 120.4

161.,1 103.,3 116.1 159.5 104.,0 157. 8 107. 9 130.0

159.,1 104..5 128.9

92

135.7 123.2 116.7

166..7 101,.0 163.,6 112.,0 131.7 104.7 153.,4 138. 8 153. 4 104.7

91

164.2

114. 8 122.3

93,.6

162..4 112,.1

166..4

94.9
104.,3 128.1 110.3 149.,1 149. 8 110. 0 120.4

30,89

C-6' Ref.

90

161,.7 104.,8 165 .2

165,.0

C-4'

148.,9 149. 5 112. 3 120.6

C-3'

90

112.5

C-2'

115.6 144.,2 145. 3 114. 5 120.8

93.,0 165,.1

94. 9

93. 6

93. 8

93. 7

93. 7

C-l'

115.7 146..6 146.7 115. 2 120.2

169.,9

159,.6 108.,6 163,.0 107 .8

159.5

162..2

164,.2

165..1

163..1

162..4

159..3

163,.6

163.,0

163.,7

162,,5 106.1

161.,8 104. 8

143.,8 114. 8

155.,6 108. 8

129.,1 110. 9

128.,9 110. 9

C-10

161. 7 103.,7 129.9

C-9

162.,5 102.,2 128.1

93,.1

C-8

96,.0 159.,4 110.3 128.1

165.,7

C-7

97. 1 163.,5

93. 8

C-6

129.,7 110. 5

162.,4

164.,4

164.9

163..7

C-5

120

121

OMe
OMe
3

MeO,

R 0

(3.144)
(3.145)
(3.146)
(3.147)
(3.148)
(3.149)
(3.150)

R'=R2

'*

= R = R

= Ht

( 3 . 1 5 2 ) R=H

taxifolin

(3.153)

R=R3=R4= HR
T 2 =M e
R = R 2 = R 4 =H
2

FR 3 =
4

OMe

M, e

R=Ac

OR

padmatin

R=H,R =R =R =Me
2
3
4
R'=Ac,R =R =R =H
2
4
3
R ' = A c tR = R = H , R = M e
2
3
4
R'=Ac,R =R =R =Me

R O

(3.156) R'=R =R =H,R =Me cedeodarin

1
2
3
( 3 . 1 5 7 ) R =R = H f R = R = M e
2
3
( 3 . 1 6 2 ) R ' = R = R = H , R =OH d i h y d r o m y r i c i t i n (ampelopsin)
1
3
2
( 3 . 1 6 3 ) R = R = H , R = M e , R =OMe
2
3
4
(3.164) R ' = A c tR = M e , R = H , R = O M e
2
3
4
(3.170) R ' = R = H , R = M e , R = 0 H cedrin

OH

OMe
(3.158)

R=3*-OH

(3.159)

R=3*-OH kushenol

kushenol

OR'

" ' , ,

2
^
( 3 . 1 6 5 ) R ' = H , R = S 0 3K . m y r i c a t i n
2

(3.166) R'=R =Me

Q H

OH
(3.167)

,. 160)

R ' = 3 ^ - O H , R = H , kushenol
,
2
161) R = 3 o c - O H , R = H , k u s h e n n o l
2
168) R ' = 3 j 9 - O H f R = C H 2 C H = C ( M e ) 2
kushenol

4
OR'

R = C H 2 C H = C ( M e ) 2 kushenol L

(3.169)

suphoronol

122

the
of

C-2

aryl

axial

The
shielding
of

conformation

stabilization through

chemical

pattern

(3.135)
-2.6

lead

and

effects
are

to

-1,5;

madendrin

+8.7;

(3.135)

and

95.1

and

8.80.1

p p m OL - e f f e c t
at

either

96.4

methyl

substituent.
to

(3.151),
C-5

the

C-8,

most

at

kushenol

resonates

at

93.70.1

The

ppm

mundulinol

resonances

159.10.1,

[45].

resonances

Such

absorb

at

159.9,

appears

3.167.

at

Such

be due

of

to t h e
The

f lavanonols,
deduced

by

ring

of

effect

of

geranyl

bonanniol

to

and

C-5

to

C-10,

-1.2

6-methylaroappears

C-6

shows

C-8

resonance

thus

showing

C-8

due

7.0-7.3

to C - 6

ppm

cor-

3-hydroxyglabrol

of o x y substituent

at

(3.159),

substituent
C - 6 , as

at

kushenol
C-8

being

position

unsubstituted,

108.1,

(3.154)

substituent,
Rt

resonate

and

100.0

ppm

substituted

159.7

155.7

101.6

ppm

in

3.142

in

the

can

only

not

methylation

(3.136)

of

pyrano

and

as

ring
C-6

bonanniol

C-8 signal in the

appears

at

105.7

and

be

5-OH

0.1,

(3.167)

[93].

Thus,

comparison
but

by

may

to
the
also

system.
in

two

(3.137) have been

c o u p l e d 13 C s p e c t r u m

proton

116.4

explained

group

thus

respectively

kushenol

and

coplanar

6",6 -

C-8 isoprenyl

position

C-8

possess

C-10

160.40.1

substituent

m u l t i p l i c i t y of t h e

The C-6 resonance

absence

C-9,

(3.144)

C-8

shielded
of

e x i s t e n c e of t h e
site

on
In

lupinifolinol

system

162.6,
ppm

shift

para

-1.0;

at

The

in 3.144,
at

alkyl

C-6

substituent

(3.156), and

position.

while

6,8-diisoprenylated

108.8,

upfield

consideration

ppm

and

102.70.1,

about

in

resonance

the

at

[61,93,94].

(3.142)

in

and

kushenol

c a r r y an

corresponding

108.80.1,

to

exhibit

taxifolin

ppm

meta e f f e c t

C-6

due

108.50.6

to

105.7

ppm

shifted
the

(3.158),

(3.161)
at

C-8,

6-methyl

flavanonols.

95.1

negligible

ppm
I

-6.5;

C - 9 , +0.4

at

cedeodarin

at

of

result

6-methylaromadendrin

The

0.0;

carbons

Thus methyl substitution

upfield

112.1

dimethyl-(2",3":7,6)-pyrano
ring

or

carbon

Kushenol

C-8 resonates

in

whereas

C-alkylation

in

C-7,

C-6 resonates
ppm

ppm

The

[92].

and

thus

methyl

C-8 appears

position

(3.160)

[55].

-1.6;

cases.

The
as

comparison

5,7-dihydroxylated

in 3.128

about

8.9;

in

104.8

in

ppm

shielding

respondes

at

probably

ring

[84,88].

(3.156)

C-7,

in respective

appears

C-8

C-6, +

[89]. The methyl substituted

atS95.4

and

1.0;

and

substituent

respectively

cedeodarin

C-6,

ring A

flavanones.

methyl

is

interactions.

the

t h o s e of
a

C-5, +
ppm

of

2,3-cis-flavanonols

of

to
by

shift

case

C-5,

ppm

(3.128)

C-10, +0.3

in

shifts

similar

aromadendrin

in

hydrogen-bonding

ppm

C-geranylated

in 3.136

and

3.137.

123

The

differnce

ortho

effect

catin

3.165

in

para

5-7

et^ a K

as

absorb

and

[96]

3'-sulfate

at

147.2

related

ppm

shifts

in

ppm

These
C-2

significant
(C-2 ,

157.4-165.8
reveal

and

about

and

because

of

to

the

quaternary

of

C-3 resonance.

field

resonances

102.3-113.7

862

their

sp

The

ppm

(Table

C-5
is

appearance

of

(3.173)

existence

of

and

resonances

and

5-OH

+0.5,

C-2

ppm
and/or

C-6',

shifts

group

absorbing

at

Therefore
between

[11,13,14,23,87,97-167],
of C - 2 a n d

2,3-olefinic
resonance

and

C-3

bond

also

thus

resonances

also

methine

(C-4) thus

at

C-5 position

hence

resulting

existing

characteristic
at

This
of

results

behaviour

lead

to an

appears

up-

between

+5.9

to
ppm

causes

5.51.5

the

appearance

to
It

is

between

keto

feature

in

because
group

be

exemplified
flavone

(3.178)
+0.8,
in

case

and

of

3.190

of

intra-

(C-4)

the

and

5-hydroxy

(3.190)

+4.5 ppm
for

relative

comparison

with

chrysin

-2.0

of

position

by

(3.171)

with

ppm

5-hydroxyflavones

1.50.8 ppm u p f i e l d

can

unsubstituted

results

and

where

in c a s e

of

C - 2 , C - 3 and

C-4

[87,107].

But
a

ortho

observed

f lavanones.

[26,97,103,104,110,113].

interactions

102.0 and

[138].

are

for

[73,85].

the

resonance

of t h e
108.6

C - 3 i n 2 ' - and

ppm

[97,

when

hydroxyl

downfield

shift

6 - u n s u b s t i t u t e d

102-104,

e.S'-pentamethoxy-S^'-methylenediqxyilavone
100.4

these

myri-

C - 3 ' and

noted

of 2 , 3 - O l e f i n i c b o n d

C-2

7-hydroxyflavone

-1.2

been

both

type

shifts

presence

of t h e

Another

respectively

between

3.3)

resonance

ppm

The chemical shift

usually

(Table

hydroxy

flavones.

of

olefinic

carbonyl

the

C-4

bond

C NMR c h e m i c a l

as

the

3.137.

which

to 3.162

of

the

of C - 3 r e s o n a n c e

5-unsubstituted

3.173

the

hydroxyl.

to

flavone

of

182.50.7

hydrogen

(peri)
the

of

the

to

3.3).

presence

shift

molecular

of

due

FLAVONES

The
of

in
has

C-6')

downfield

presence

175.2-183.4

resonance

ppm

nature.

ppm

C-4

deshielding

is

flavanonol sulfate,

3.162

relative

are

behaviour

132

downfield

galloyl

C - 4 , and

ppm

643

shift

The

2,3-dehydroderivative

C-3

compounds

C-5 position in

p o s i t i o n in 3.165

are

and

two

dihydromyrecetin
1

carbon

deshielded

at

characterized

of

3.4

both

these

of m e t h y l a t i o n of h y d r o x y

Nonaka
C-5

chemical

or

occurs

106-108]

(3.328)
methoxyl
to

where
group

between

flavones

except

110

it
is
and

in

is

5,6,7,

absorbs

at

attached

to

115.5

ppm

124
[102,103,140].
flavones
of t h e
shift

and

In
at

hydroxy
of t h e

general,

ca.

112

C-3 absorbs

ppm

All

carbon

ca.

115

ppm

2 -methoxyflavones

of m e t h o x y s u b s t i t u e n t

C - 2 resonance

at

in

at

in

2' ,6'-dimethoxyl

[103,140].

C - 2 ' position

The

also causes

presence

an

upfield

[102].

resonances

of

flavone

were

assigned

for

the

first

time
13
by
N a t h a n et_ a K [ 1 0 ] b y c o m p a r i s o n o f t h e p r o t o n n o i s e d e c o u p l e d
C
spectra
of f l a v o n e ,
5,6,7,8-tetradeuterof lavone,
2 ' , 3 ' , 4 ' , 5 ' , 6 ' -pentadeutero
o o k tehr e
fblaasvios n e ,of 4 ' - b rCo m -o f l aHv o nsep l i(t3t .i1n8g4s) of
a n d v ba yr i otuhse ac da dr bi toi no sn, o fK itnh ge s bEuur y( d pamn )d3 . LUn
13 1
13
[102] a s s i g n e d
C r e s o n a n c e s of a l l t h e p o s i t i o n a l i s o m e r s of m o n o m e t h o x y
13
1
f l a v o n e a n d W e h r l i [ 98 ] i n v e s t i g a t e d t h e
C - H couplings in h y d r o x y l a 13
ted

flavonoids.

Using

unsubstituted

flavone

studies

the

infer

ytterbium
(3.171)

shift

were

preferred

reagents,

confirmed

binding

of

the

C
by

signal

assignments

several

LSR

to

the

workers.
keto

in

These

group

(C-4)

[12,13,99].

13

I i n u m a et_ a h
c a r r i e d out d e t a i l e d
polysubstituted
flavones and noted that the
and

correction

NMR
at

shifts.
C-4

C-9

of

C-2',6'

be

ppm)

-2.2;

and

(3.509)

by

be

the

has

Section
shifts

1.4)

0;

from

+2.6

the

be
the

were
of

and

moreover
resonances

flavone

(Table

NMR a n d
of

moiety

C-8,10

-11.6;

and

the

- value
a

from

chemical

(C-l

+2.5;

the

observed

substituent

attached

synthetic

brickellin

studies,

which

was

6,7,2',3',4'-pentahydroxyflavone

earlier

supported
with

as

structure

3.341

identified

as

for

and

these
earlier
[140a]

agehoustin

3.342

group
by

the

hispudulin

at

respectively

5,6-dihydroxy ,7-methoxy

5,7-dihydroxy,6-methoxyflavone

methoxyl

3.3).

proposed

confirmed

as

of

as

carbonyl

3.2;

calculated

itself

structure

negletin,

revised

appearance

the

their

2' ,5-dihydroxy-3,4' ,5' ,6,7-pentamethoxyflavone

[139]

the

C-6

COCHCH2

hand,
was

calculating

taking

-2.6;

S C S of

other

benzopyrone
13

upon

for

obtained
(C-5,7

ppm)

proposed

to

necessary

the

On t h e

C-4

the

structure

of , r i n g - A

substituted

ppm).

Similarly

been

of

calculated

Based

found

[141].

basis

were

value

OL

5,6'-dihydroxy -

and a g e h o u s t i n
[140].

flavone

values

the

regarding

revised

on

The

and

C-3',5'

to

later

are

(128.7

(B r i n g ) .

have

supposed

value)

was

shifts

benzene

authors

(o

C O C H C H 2,

benzene

chemical
to

The

to

+28.5

shift

factor

C NMR s t u d i e s on mono a n d
parameters
( o(, a n d
values)
13

60.0

(see

resemblance
(3.251)

and

of

(3.220)
Chapter
the

other

on
One,

chemical
similarly

125
The
3.189,

Nathan and
nances

due

to

to

chemical

shift

flavone

the
of

The
at

(3.190)
4.8
be

C-8)

in

more

shifts

and

C-8

at

the

site

of

downfield

quite

The

resonances
and

position
in

upfield

in

94.4

location

techniques.

relative

to

estabilishing

C-8

the

absorbs

of

the

in trans

methoxyl

is

not

However,

at 9 4 . 4

group

easy

these

to

prenyl

side

resonance

160].

Thus

at

chain

at

The

23.70.2

as in other

C-3

two

the

ppm,

exist

possessing

the
(5,6-

7,8-naphthofla-

C-6

either

absorbs

C-8

[110]

[114].

of

other

pattern

i.e.

very

well

can

unsubstituted

and

or
was

position

basis

substitution

of t h e

(C-6

resonance
(3.230)

the

observation

C - 6 or

8-methoxy

chry-

C-6

This

tephrostachin

of

e.g.

thus

C-alkylation

at 6 9 9 . 0

kuwanon

methine

(C-6) in

at

results

to

15

ppm

shift
of

as

quaternary

behaviour
ppm[144-

noted

3-prenyl

resonances

appear

possess

117.1-123.2

x, - e f f e c t

range

the

at

3.370)

but

C-2

for

nonprenylated

substituent
at

the

and

C-4

resonates

same

positions

flavonoids.
characterized
13

several

residue.

spectrum

of

novel

(3.358),

these

moracenin

type

106.8-108.0

ppm

of

flavone derivative

Therefore,

(3.359)
at

and

contai-

least

thirty

A l l of

these

moracenin C (3.356),

substituent
[152-158].

at

compounds.

moracenin (3.355),

dihydrochalcone

C - 8 to a b s o r b

other

3.369,

C-3 resonance

about

resonance

dihydrochalcone
the

3.362, 3.356,

chemical

whereas

as moracenin A (3.354),
(3.357),

of

However,

at

types

which

of

shows

same

et^ a K

in

position

absorption

prenylated

condensed

nances

(3.345

methylene

Nomura
ning

at
and

C-prenylation

almost

flavones.

In

carbons,

substitution

[106]

d e t e r m i n e on

( C - 8 ) i n c a s e of f o r m e r

flavones

of

absorb

by
reso-

[124].

Several

C-3

fifteen

resonances.

ppm,

resonance.

site

6 - m e t h o x y - and 5 , 7 - d i h y d r o x y ,
b e d i f f e r e n t i a t e d b y t h e 13 C NMR c h e m i c a l s h i f t s

c a s e of l a t e r

the

benzo

(3.187-

assigned

5,7-hydroxyflavones,

5,7-dihydroxy,
which

angular

ring-

105.6

respectively

p o s i t i o n s 93.1

5,7-dihydroxyflavones

spectral

to

the

the

6,7-naphthoflavone

99.2

significance

at

as
were

aromatic

of

5,7-dioxygenated-6-C-alkylatedflavones.

observed

in

reflects

well

in addition

four

chemical

ppm,

as

ppm).

C-6

of

(3.194)

napthoflavones

possess

in

C-2 also

appear

ppm

may

moiety

1100.5

vone 108.30.3

linear

These compounds

difference

naphthoflavone,

in

3.278,3.306-3.308)

Santillan [105].

addition

sin

NMR s i g n a l s

3.200-3.202,

kuwanon

C-8 position

resosuch

kuwanon G

which

(3.362)
results

124 .6
124 .8

164 . 1 105..6 182..9 159 .8

108..7 177..8 159 .4

162 .4 107..3 176..9 118 .0

106..5 176..1 126 .3

107..1 178.,0 114 .2

162 .6

162 .5

162 .6

162,.6

162,.6

160,.8 111.,1 177.,3 125,.2

160.6

162,.8 107.,5 178.,0 125,.4 124,.9

3,.171

3..172

3..173

3..174

3..175

3..176

3.,176

3.,177

3.,178

3.,179

3.,180

3.,181

3.,182

3.183

104 .8
114 .9

126 .9

156 .5

134 .8

109 .8

107 .2

125 .3

124 .9

125 .2

163..0 105. 9

3. 186

177. 9

124,.8

125,.2

C--8
C-l'

C--2'

C-3'

C--4'
C-5'

C--6' Ref.

123. 7 131.5

155..7 123. 4 131.1

156,.3 124. 1 131.5

126,.3 129.1 131,.8 129.1

153..6

122. 7 131.2

126..3 128.9

131,.0 128.6 125..6 102

131,.9 128.9

125..8 128.7 131,.2 128.7 125..8 103

125..6 128.6

119..4
-

126..1 128.9

131,.3 128.9

126..1 102
126.0 128.9 131,.3 128.9

126..0 87

120. 7 157..8 111.6

132..2 120.5

132,.6 119.5

129..1 102

128..6 102

133.,8 117.9

156.0

123. 8 130.6 127.,6 132.2 126.2

132.2 127.,6 98

133..2 117.,9 155..9 123. 7 132.8 111..5 159.7 116..9 129.8 118..5 102

133..3 117..8 156..2

134..1 118..5 155,.9 123.2 117.8 156..7 117.1

116..1 148..8 146..0 124. 0 131.6 126..1 128.7 131..2 128.7 126..1 102

163..7 100..2 157..7 117. 6 131.6 125..8 128.7 131,.1 128.7 125..8 102

161..7 102..4 157..3 116. 0 131.1

145..2 118..0 156.. 1 121. 5 131.7 126..4 129.2 131,.7 129.2 126.,4 103

123..6

122..6 119..5 150..1 123. 8 131.0 125..8 128.7 131,.3 128.7 125..0 101,103

123..8 117..6

133..4 106..2 157..9 114. 0 131.9

135..6 110..8 155..8 110. 3 130.5

126..3 97

101

126..3 14

126,.3 129.0 131,.5 129.0 126..3 100

126,.0 128.8 131 .3 128.8 126..0 99,11,102

117..7 155..4 122. 6 131.3 127..5 128.4 131,.4 128.4 127.5

134,.2 118..5
134.0

C-10

156,.3 124. 0 131.8 126,.3 129.0 131 .6 129.0 126..3 13,97,98

C--9

,
117..9 156 .0

133,.7 118.1

133,.5

133,.7 118,.1

C--7

133.,9 118.,3 155.,6 123. 4 121.7 128.4 116.0 161..0 116.0 128..4 104
125..3 124,.7 133.,0 117.,7 155.,8 123. 7 131.9 127.,7 114.2 162..1 114.2 127.,7 102

125,.6

176.,9 125..3

162,.0 107.,5 177. 9

163,.1 104. 9

3.185

112.,5 178.,7 125,.4 124,.6

107.,2 177.,4 126 .7 114 .1

106..7

3. 184

162 .4 105..8 176..6 105 .2

162 .4 106..5 176..8 117 .6

160 .6

125 .5

117..7 174,.5 125 .3

106,.9 177.2

163 .4 107,.0 178,.2 125 .8

124 .9

107,.3 178,.0 125 .4

163.0

3,.171

C--6

3,.171

C--5

107,.6 178,.4 125 .7 125 .2

C--4

163 .2

C--3

C -2

of flavones*

3..171

Str.No. Solv.

Carbon-13 NMR chemical shifts

Table 3.3

126

127

R'

(3.171)
(3.172)
(3.173)
(3.174)
(3.175)
(3.176)

=R2=RJ=H

=R =H
=COOMe,R
3
2
=R 3=H,R 2 =OH
=R 2=H,R 3=OMe
=R 2=H,R 3 =Me
=R =H,R =OMe

(3.
(3.
(3.
(3.
(3.
(3.
(3.

177)
178)
179)
180)
227)
228)
229)

R'
R'
R'
R'
R'
R'
R'

=R =H,R =Me
3
2
=R 3 =H,R2 =0H
=R 2=H,R 3=OMe
=R 2=H,R
=OMe
3
=R =R =0H, norwogonin
2
3
=0H,R 2=R =0Me3
=0H,R =0Ac,R =0Me
OR

(3.181)
(3.182)
(3.183)
(3.184)
(3.206)
(3.216)
(3.217)
(3.241)

R'1
R
R'
R'
R'
R'
R'
R'

=OH,R =R
=H
2
3
=0Me,R
=R
=H
3
2
=R 2=H,R 3=OMe
=R 2 =H,R =Br
3
=R =OMe,R
=H
2
3
=H,R =R =0H
2
3
=H,R
=R
=OMe
2
3
=R =R =OMe

(3.187) R ' = R 2 = R 3 = H
f
2
3
( 3 . 1 8 8 ) R =OMe,R =R =H
3
2
(3.189) R ' = R = H , R = O M e
2
3
(3.306) R ' = R = H , R = O M e

(3 .185)
(3 .186)
(3 .207)
(3 .208)
(3 .209)
(3 .210)
(3 .211)

R =R =H
2
R' =H,R =Me
2
R' =0H,R 2=H
R' 1 =0H,R =Me
2
R" =OMe,R2 =Me
R' =OMe,R 2=H
R' =OMe,R =Ac

(3.190)
(3.191)
(3.192)
(3.193)
(3.203)
(3.204)
(3.233)
(3.234)
(3.236)
(3.237)
(3.238)

= O H c3 h r y s i n
R'=R =H,R
2
R ' = H3 , R =OMe,R
=H
2
R'=R =
H , R =2 C H 2 C H 2 C H 2 C H 3
3
R ' =R 2=H, R 3 = p - methoxy phenyl
R ' = R2 = H , R3 = 0 H
R'=R =H
, R3 = O M e
2
R ' = H , R = 2R =3O H , apigenin
R=Me,R
=R =OMe
1
2
3
R =H,R2 =OMe,R
=OH,genkwanin
3
R ' = H , R =2R = O H 3, thevetiaflavone
R'=H,K -GII,R -OMe,acacetin

163..5 105..6 178..6 129..3 130..0 135..6 114..0 152.,0 122. 4 121,.5 128,.8 131.5 128 .0 131.5 128,.8 105
99..3 156.,5 117.,0 131..6 126,.4 129.2 131 .8 129.2 126..4 103

164,.6 106,.4 183,.2 156,.9 109,.5

162..5 107.3

162..4 106..5 176.9

163.,0 107..1 178.,3 105.,1

161.,7 106..1 176.,1 117.6

161.,5 108..0 177.,3 120.,1 128.,7 135.,3 119..6 152. 6

162.,1 108..2 177.,9 119..4 127..2 127.,5 120..3 152. 8

162.,3 108..6 178.,0 124..8 129..0 131..9 120..5 152. 5

165.,4 103.,9 183.,4 156.,4 108.,0 136,,2 111..4 160.0

164.,1 104.,0 182.,5 155.,7 106.,9 135.,1 110..5 159. 7

160.,5 111..8 178.,3 127.,1 114.,2 164.,1 100..4 158.0

161.,7

D+W

D+W

C+D

3.193

3.194

3.195

3.196

3.197

3.198

3.199

3.200

3.201

3.202

3.203

3.204

3.205

3.206

3.207

3.207

148 .4 109,.7 160. 6

131 .6 126 .4 129.1 131 .8 129.1

104
126,.4 108

117. 6 131..4 126,.2 129.2 131 .9 129.2 126..2 103

105. 0 131,.6 126.5 129.1 131 .9 129.1 126,.4 108

118..7 101

131 .2 128.9

125..9 105

163

114.5

128..1 97

128,.0 109
128,.3 104
116.1
160.9

160 .7 115.9
116. 3 122..0 128 .3 116.1

134.,3 118..3 155. 9

162.,5 104.,5 176.,3 126.,4 114.,7 162.,4 102..4 157.,4 116. 1 121..8 128 .0 115.9

177,,6 125.,4 124.5

162.,7 104.,7 176.,6 126.,6 115.,0 162.,7 102..7 157. 6

116..0 103

121. 1 121..1 158.3 112.7 132 .3 120.8 129..2 11

109. 9 119..2 128 .1 114.5

110. 5 121.,9 129 .2 116.7 161 .7 116.7 129..2 97

125. 0 131..0 126 .0 129.0 131 .2 129.0 126..0 105

124. 8 131..6 125 .9 128.9

123. 4 131..2 125,.6 128.7 131 .1 128.7 125..6 105

119. 6 131..0 125,.7 128.7 131 .0 128.7 125..7 103

124. 7 133..2 111,.8 160.1 117 .1 130.1

123. 0 111..2 147,.1 153.0 111 .2 120.5

110.,5 156.,0 136..2 149. 5

123..8 151. 2

95.,0 149..3 140. 7 124.1 130.8 125,.5 128.4 130 .8 128.4 125..5 156

157 .1 124.7

161.,1 105..7 175,.9 104.,7 156..2

123..6 113.,8 161.,4 109..6 154.8

176.,4 125..7 125..3 162,.5

106

157.,5 103.,9 130..7 129 .0 126.3 131 .9 126.3 129..0 107,154

92,.8 157.,4 105.,0 130..6 126 .5 129.2 132 .1 129.2 126..5

94.1

94.. 4 159.,8 103.,9 130..8 126 .5 129.3 132 .1 129.3 126..5

152 .2 111,.7 160. 6

98,.2 165..4

99,.0 164..6

164 .3 106 .8 183,.2 156,.5 109,.1

163,.5 105,.4 182,.1 161,.3

125..5 105

130 .8 128.5

133..8 117,.7 157.,5 117.,0 131,.0 125 .7 128.7 131 .0 128.7 125..4 105

99,.2 164.5

131..9

157.,2 115.,9 130,.8 125 .5 128.5

105,.3 182..0 161..4

160,.1 109,.6 179..5 124.9

160,.0 109,.5 179,.7 131..8 125,.2 134..4 114.2

3.192

126..0 105

C-6' Ref.

3.191

C-5'

163,.1 105,.1 181..8 161..5

C-4'

163.5

C-3'

C-2'

C-l'

3.190

C-10

157.,2 117. 2 131,.3 126 .0 128.9 131 .3 128.9

C-9

3.190

C-8

C-7

3.189

C-6

160,.7 110,.4 180,.1 130,.5 130..4 135..7 117,.5

C-5

C-4

C-3

3.187

C-2

3.188

Str.No. Solv.

128

129

(3.200)
(3.201)
(3.202)
(3.278)
(3.307)
(3.308)

R = M e , R = 0 M e , R =R"*=H
1
2
3
R =H t R = O M e , R = M e , R =H
3
2
4
R'=R =OMe,R =R =H
2
3
R ' = R * : =OMe R = R = H
4
2
3
R ' = R : =H, R = R = O M e

(3.205)
(3.212)
(3.213)

Rv ' = O M e , R = R = H
3
2
R'=R =H,R =0Me
f
2
3
R =R =H,R =0Me

R ' = R = R = R =R =H
2
3
R ' = O M e . R = R = R =R =H
3
2
R'=R =R^=R =H,R =OMe
2
3
R ' = R = R = H $R = R ^ = 0 M e
2
3
R ' = R = H R - R =R =OMe
3
4
5
2
R ' = R = R = R = O M e , R =H

(3.195)
(3.196)
(3.197)
(3.198)
(3.199)

(3.218) R ' = R = H , R = M e
2
3
(3.219) R ' = H , R = R = M e
3
2
(3.220) R ' = R = H , R = M e ( n e g l e t i n )
f
2
3
(3.221) R = R = R = M e , b a i c a l e i n
trimethyl ether

(3.222)

98.8

183,.3 162 .6

162 .6

3.217

163 .2

159 .9

159 .2

159 .4

160 .1

163 .2

163 .5

3.221

3.222

3.223

3.224

3.224

3.225

3.226

3.227

3.228

159 .6

159 .9

163 .2

162 .0

3.220

3.221

175 .4

164.1

3.216

163 .9

161 .7

3.215

160 .0

3.214

160 .4

3.213

3.219

162 .7

3.218

124.6

105. 8 176..6 125,.0

161 .9

C+D

3.211

105.1

104.7

108.6

108.0

107.9

108.0

106.9

105.1

107.2

108.3

104.7

105.4

105.8

105.4

106.9

113.6

113.4

112.2

107.3
124 .5

152,.5

182..5 149,.0

182.,4 145,.8

176.,1 151,.6

175.,9 152,.0

176..1 151,.3

175..5 150.8

176,,3 144,.9

181..8 155,.3

175,.2 153,.5

177.0

182..2 152,.6

182..6 152,.9

177..9 125 .6

176..4 124.7

176..9 125 .1

176..6 124 .8

176..6

177,.4 126 .9

96.2

98.9

102.6

96.9

93.8

93.9

139.9

104.7

139.6

140.4

130.7

132.6

125.1

124.1

124.4

124.7

124.3

114.3

114.3

114.6

3.212

176,.3 126 .1

176,.4 126 .2

C+D

105.3

162 .4

162 .7 104.7

114.6

C-6

3.209

176..4 126 .5

C-5

3.210

105.2

C-4

161 .9

C-3

C-2

3.208

Str.No. Solv.

C-8

101.0

117.6

118.2

94.8

96.7

96.3

94.4

158..8 128.7

153..9 125.2

147.,4 134.1

129.0

156..6 130.1

156..1 130.0
155..6

158.4

155,.6

156 .1

155 .1

155 .6

156 .2

155 .3

157 .7

157 .4

157 .5

157 .5

C-9

156 .9

153 .3

155,.0

155,.2

155,.9

155 .3

138,.4

156 .3

151,.2

154,.5

157 .3

90. 6 153 .2

92.8

118.1

118..5 149.0

158.7

157..2

157,,7

152..6

158.8

166 .1

133..6

134..4 118.4

133..4 117.8

133..9

133..9

133..4 117.8

164,.0 100.3

163..7 100.8

163..9

162,.7 102.6

C-7

C-l'

C-4'

C-5'

C-6' Ref.

159,.1

132 .3 104. 1 137.,7

103

35. 5 209 .3

35.,5

37,.0 169

126..1 129. 0 131 .8 129. 0 126..1 27

37 .0

110..5 149. 3 152 .2 112. 4 119..9 97

114,.0 145. 8 149 .5 116.2 119..4 97

104,.0 160. 4 103 .1 160. 4 104.0 103

151,.6 114. 0 120 .0 152. 0 111..5 103

104.1

103

130.4

131.1
102..2 130.9

103.,7

112..9 131.0

107..6 131.3

108..2 131.3

107..4 130.0

103..3 130.8

104.7

111..8 130.9

112.,9 131.5

128. 8 131 .8 128.8

126..2 111

132 .1 129.,2 126,.7 113

126,.4 129. 4 132 .3 129.,4 126..4 113

126,.7 129.2

126..1 129. 3 131 .8 129.,3 126 .1 112

125..9 129. 3 131 .5 129. 3 125..9 112

125..9 129.2 131 .5 129.2 125..9 112

125..4 128. 7 130 .9 128. 7 125..4 103

125..6 128. 8 131 .2 128. 8 125..6 103

126.2

125..4 128. 4 130,.9 128. 4 125..4 103

125..9 128. 9 131 .2 128. 9 125..9 17

104..7 131.4 126,.4 129. 1 132 .0 129. 1 126..0 110

106..2 131.1

71.3

123..7 123.3

123..6 122.9

122..8 132.0

122..8 120.2

98. 7 160 .9 105. 8 129.,7

127,.2 122. 1 152 .0 122. 1 127..3 11

128..1 115. 9 160 .8 115. 9 128..1 11

123..1 110.4 157.7

122..7 109.9

117,.6 129.2

105.,8

C-3'

127..9 114. 5 162 .1 114. 5 127,.9 104

C-2'

123.4 128..1 114. 6 162 .1 114. 6 128..1 104

117..2 121.8

117.2

116..2 123.5

C-10

130

131

OH

(3.223) R ' = O M e , R = H
2
(3.224) R ' = H , R = O M e n o r w o g e n i n
trimethyl ether
2
(3.225) R ' = H , R = 0 H
2
(3.226) R ' = H , R = 0 A c

(3.230)

OMe

trans tephrostachin
3
R
,OMe

(3.231)

R'=OH,R =H,R =Me

2

(3.232)

R'=H,R =R =OH

(3.246)

R=Me

(3.247) R=H

(3.235)
(3.240)

R'=Me,R =OH,R =H
2
3
R'=OH,R =H,R =OMe

162.0

160.3

3.246

162.4

163.7

160.2

3.245

3.243

3.244

160.9

161.2

3.245

3.242

104

164.7

3.241

111

161.2

3.239

3.240

103

107

106

106

105

113

111

110

103

163.9

164.6

107

103

103

106

106

102

104

3.238

160.4

163.4

164.6

160.0

109

1 0 3 .1

3.238

3.237

3.235

3.234

163.8

3.233

3.236

165.5

DfW

3.233

3.237

164.2

160.1

161.6

D+V;

158.6

113

175. 6

176

177

177

176

176

176

182

178

182

182

175

181

182

178

175

181

183

182

182

176

177

108 .5

161.1

3.233

3.231

182

105

164.2

C-4

C-3

C-2

3.232

3.230

3.229

Str.No. Solv.

143 .7

124.9

125 .5

125 .4

124 .5

125

124 .4

155 .7

104 .7

161 .8

162 .2

159 .0

161 .6

157 .7

141 . 2

158 .8

161 .1

162 . 0

161 .5

161 .6

150 .5

160 . 0

155 .5

C-5

4
2

137

124

124

125

124 .5

124

124

109

156 .7

98

99

96 .4

99 .0

98 .2

116 .5

115 .9

98 .8

1 0 0 .3

99 .1

98.8

146 . 4

9 3 .1

106 .0

C-6

150

133 .5

134

134

133

133

133

135

124 .5

165

164 .8

162 .4

164 .3

165 .6

160 .9

163 .4

164 . 1

164 .9

163 .9

164 .5

133 .6

162 .2

149 .1

C-7

137

118

118

118

117

118

118

110

124

92

94

95

94

92

100

93

94

95

94

94

117

108

132

C-8

147

155

155

155

155

155

155

159

153

157

157

159

157

161

158

159

157

113

123

123

123

122

122

122

109

126

105

104

106

103

105

130

126

126.5

121. 1

103. 7

125. 1

108. 0

122

119

121

123

121

122

121

123

114.2

121

7
122

122

121

117

117

132

130

C-l'

108

103

105

158.7

103

111

107

109

104

C-10

157

157

149

155

149

C-9

147 .7

125 .6

1 0 4 .1

104

105 .9

158 .6

140 .8

152 .0

110 .5

128

152

153

146

91

155

141

149

151

116

130

140

140

137

162

102

155

114
152

161

162

160

114.8
128 .8

128 .4

162

161

3
6

161

161

161

161

161

132

115

114

116

1
3

131

132

7
0

132

128

152

153

146

91

153

108

119

123

116

114

115

114

116

114.2

114

116

117.3

116

119

119

129

129

C-5'

C-4'

127 .7

128 .3

128 .8

114

114

127 .2
127 .5

116

117

116

117

116

129

129

C-3'

128 .4

1 2 9 .8

128 .6

156 .8

153 .0

126 .7

126 .7

C-2'

125

104

104

105

158

103

118

120

128

12

128

127

128

128

127

103

103

104

104

103

156

103

130

101

58

31,117

31,117

58

31,117

87

103

116

30,133
4

154,155
8

115
7
6

103

114

8
9

112

127.2

128

129

128

128

127

126

126

C - 6 ' Ref.

132

151 .8
152 .8
151 .8
151 .0
141 .1
144.7

105.,5 185 .5

163,.8 102 .4 181 .8

163,.7 102 .4 182 .1

111 .4 175 .4

108 .4 183 .0

111 .2 176 .4

181 .8

175 .2

108 .6

177. 3

161,.5

157,.9

161,.6

158.2

161..2 108 .6

3.249

3.250

3.251

3.251

3.252

3.253

3.254

3.255

3.256

D
D

3.262

3.263

108,.6

182 .5

151,.4
156 .2
144 .4

162..1 106,.7 175 .8

163..1 103 .4 181 .9

162..6 107 .0 176 .4

3.266

3.267

3.268

149,.7

182 .1

163..8 102 .9

140 .2

164..1 106,.4 182 .9

3.264

156 .3

152 .8

155 .8

3.265

161..3 109,.0 182 .2

161..5

157..7 112,.6

176 .1

3.261

156 .8

155 .1

182 .4

3.260

161..8 109,.6

157..7 112,.7 176 .0

3.259

156 .4

109 .6

150 .8

182 .1

157,.3 112 .3

161..3

3.258

148 .6

153 .6

3.257

182 .3

162.,6

175 .4

105 .8

161,.6

152 .0

181 .5

102 .9

163,.1

3.248

145 .8

182 .6

163,.4 104 .9

C-5

C-4

C-3

C-2

3.247

Str.No. Solv.

114 .1

99 .1

95 .1

C-9

151,.8

127,.8 156,.1

139,.0

141,.7 139,.2
140..6

115,.8

157,.6

157,.7

156,.5

158,.7

155,.6

157,.4

72. 5

104,.9 120.8

105. 9
29.0

128..2 115.7

30. 1

111,.8 122.,8 127..3 114.2

122.,5 127,.5 114.0

C-6' Ref.

161..9 114.0

29. 0

30. 1 169

116.6

118 .9 127,.8 103

117. 4 156..9 117.2

127.,7 149..5

130.,8 155..3

127..9 156..5

123. 7 127,,7 114.9

114.6

103,,5 122. 9 128,.2 114.7

103..7 121. 5 128..5 116.3

141..8 138..4 108.,4 121. 0 128..3 115.8

123

162,.2 114.6

162..3 114.7

127..9 124

128..2 124

159..9 114.,9 127.7 103

161..5 116.,3 128..5 119

161..1 115.,8 128..3 156

133..0 119.,6 128.3

132..9 119.,5 128..6 113

132..7 120. 9 128,.7 122

152..8 104.2

133..4 121.,0 129..1 112

132..6 121.,0 128,.7 122

107..4 120. 0 157.,5 112.6

151..4 107..9 119. 8 157.,7 112.6

132..2 121.,0 129..1 112

132..3 119.,1 128..7 103

131..7 118.,9 127,.8 103

131..7

103,.7 119. 7 158.,0 112.7

107,.9 118. 9 155.,7 116.5

103,.6 117. 1 156.,4 116.7

104,.3 117.,5 156.0

131..6 118,,8 127,.8 103

132..4 119.,2 128..0 103

156..0 116.6

131..6 119.,4 128,.4 103

161..9 115,,9 128,.4 110

161..0 115.,7 128,.2 121

64. 5

103

127,.5 120

160..2 114.,2 127.3

104,.1 119. 6 158.,0 112.7

149..2

C-5'

132,.1 129.,3 126,.4 119

C-4'

107,.5 119.2 156..4 116.8

111,.4 117.3

105,.0 119. 4 156..7 116.9

146,.7 139..0 151..4 116..0 123. 4 127.9

157,.1

156,.6

C-3'

127.,8 149..8 103..5 117. 5 157.,1 117.3

94.3

130..0

129..1

152..1

127,.8 149,.9
129..0

C-2'

152,.4 104,.1 121. 0 128..4 115.9

158,.0

96..7 157,.0

91,.5

94,.2

91,.3

92. 6 158. 5

C-l 1

103,.6 131.,2 126,.4 129.3

C-10

151,.7 104.9

96,.7 151,.2

91..8

125,.8 148,.5

C-8

155,.7 129..9 155..1

157.9

118 .9

116 .8

153 .6

158 .6

157 .1

152 .3

165,.9

157 .1

158 .1

151 .3

C-7

99 . 1 157,.2

139 .4

99 .0

131 .4

93 .7

96.0

96 .8

99 .1

93 .9

95 .4

139 .0

139 .2

139 .4

132 .9

131 .3

131 .6

98.,0

139 .5

132 .0

132 .1

C-6

133

C-5

164.5

160 .1 107,.0 175,.6 159 .6

164 .2 103,.0

3 .272

3 .273

3.274

163,.6 104..0 181..8 161 .7

3,.276

3,.277

3,.278

3,.279

C-l'

C-2'

C-3'

C-4'

C-5'
123

C-6' Ref.

104.2 119..3 113..8 146..2 150..1 116..4 122..1 31,117

131,.9

163..6 106.,0 182.,1 144 .9

162..3 106.,4 175.,8 143 .8

164..8 102.,6 182,,4 153 .1

164..2 102.,0 181.,9 152,.5

163..9 102.,9 182.,2 152 .5

163..9 103.,0 182.,1 152 .0

3,.283

3..284

3..285

3.,286

3,,287

3.,288

3.,289

3.290

160.6

131,.9 158.,5

162..1 108.,9 183,,0 145 .6

3..282

102.,2 139..7 148..5 112..9 140..5 139.,7 103

157..2 132.,9 148..6 106.3 117..3 157..3 117..3 133..3 119..7 128..4 103
122..7 128..0 114.6 162..4 114..6 128..0 103,127

105.,7 175.,6 153 .7 139..5

157.,2

131,.7 152 ,.5

158.,5

91.,2 151..9 111.9

121..5 113..4 145..6 149..7 116..0 119..0 103

91.,3 152.,1 105.1 121..5 110.,1 150..8 148..0 115..8 120..4 120
91.,6 158,,5 105.2 121..3 110..2 148.0 150..8 115..7 120..4 128
96.,9 151.,4 111.8 121..8 109..9 147..9 149,.9 115,.6 119,.7 103

138,.0 151.,1 130.,0 147..7 125.0 123.,6 128..0 115..0 160..7 115..0 128..0 103,127
131,.4 157.,6 94.,4 152..7 104.4 121..9 113..6 146..0 150..0 116..0 119..3 58

135,.8 152.,1 132.,5 148,,1 114.6

135,.9

131,.7 150.,8 128.,2 148..2 103.2 117..8 156.,7 117..3 132..6 119..6 128..3 24

133.,6 117.,9 155..9 122.9

161..5 108.7

3..281

124,.6

161,.8 106..6 176..5 126 .7

159..9 113..3 176..3 125 .1

3,.280

182.,4 145 .6

146.5

105..7 104
137.5

115,.0 162.,7 103.,8 157..5 116.2 126..5 104..0 153..3 140..5 153..3 104..0 104

115,.1 162..8 102.,5 157..6 116.3 121.,4 105..7 146.5

163,.1 104..8 176..6 126 .8

103.8 122..9 109..5 149..0 152..0 111..8 120..1 58

94.,1 157.4

94.,0 157..5 103.7 118..7 113..1 146..9 151..2 112..1 123..3 31,117

93.,9 157..4 103.8 123..1 113..0 146..9 151..2 112..3 118..8 117,58

94..0 157..4 103.3 120..4 110..2 150..8 148..0 115..8 120.. 4 31

92..5 157..2 104.6 121..5 113..5 145..7 149..8 116..0 119..0 126

96..1 159,.1 108.2 123..0 109..1 148..9 151..5 111..5 119..2 125

94..2 157,.9

104.2 122..1 113,.8 146,.2 150,. 2 116..4 119..3 56,116

93..9 158,.4 104.0 104..0 156..7 108,.8 132,.3 102..2 158.,5 123
94..2 157,.9

128 .8 135..7 119.,9 153..0 123.8 124.0 108..5 149..1 151..8 111..1 111..5 105

98,.8 164..3

C-10

157,.7 103.9 117,.9 145,.7 146,.1 117,.9 119..3 118..6

C-9

94..0 158,.4 104.2 108,. 7 156,.8 106,.9 131,.9 106..9 156..8 119

93,.9

C-8

162,.1 107..3 177..7 120 .5

163,.4 103..9 181..9 161 .5

99 .0 164..3
99 .0 164..4

98 .8 164..2

163 .7 103,.8 181,.8 161 .6

163,.7 103,.6 181..8 161 .6

165..1

163,.5

164,.7

164,.7

164.5

164,.3

97 .9

93 .3

99 .2

99 .2

98 .9

98 .8

3,.275

161 .2

C-7

98 .8 164,.5

C-6

3,.276

103,.3 182,.2 162 .1

162 .1

161 .8

103,.3 182,.2

112,.1 181,.9

161 .9

164 .5

3 .271

182 .0 161 .8

182 .1 161 .6

C-4

3..272

112 .1

109 .1

161 .9

162 .5

3 .269

C-3

C-2

3 .270

Str.No. Solv.

134

135

R 0

OR
(3.248)
(3.249)
(3.250)
(3.251)
(3.252)
(3.253)

R ' = R = H , R = M e , R =OMe
salvigenin
.
2
3
R ' = R = M e . R = H , R =OMe
s c u t e l l e r i n te|tramethyl
ether
2
3
= R = R =H,R
OH
tJ
= R 2 = 3R = H , R
OMe
pectcJinarigenin or h i s p u d u l i n
1
2
3
R =R = H , R = M e , R =>OH
2
3
R ' = R = M e , R = 0 H , R =H

(3.254)
(3.255)
(3.256)
(3.257)

R'=R =H,R =OMe

2
3
R'=Me,R =OMe,R =H
2
3
R'=R =H,R =0Me, skulleapflavone I
2
3
R ' = M e , R = H . R =OMe

R 0
MeO
1

OR
2
3
(3.258) R =R =R' H J R = O M e
2
3
(3.259) R
R =R =H,R =OMe
2
3
( 3 . 2 6 0 ) R =R = H , R = M e , R = Q M e
2
3
( 3 . 2 6 1 ) R = R = M e f R = O M e , R =H
r
3
( 3 . 2 6 3 ) R ' = R 2 = R- = H , R = OH
( 3 . 2 6 5 ) R ' = R 2 = R 3 = H, R =OH 8 - m e t h o x y isoscutellargin
2
3
( 3 . 2 6 6 ) R ' = R = M e , R = H , R =OMe
( 3 . 2 6 7 ) R ' = R 2 = R 3 = H R$ 4 = o M e
galangustin
2
3
4
(3.268) R ' = R = A c , R = H , R = O M e

OR

(3.262)
(3.264)

R'=OH,R =R =H,R =OH

3
2
4
R'=R =H,R =OMe,R =OH
R

(3.269)
(3.270)
(3.271)

R'=OH,R =H
2
R'=H,R =OH
2
R'=H,R =OMe
3
R

MeO

R Q

MeO
1

OR

2
3
4
(3.272) R ' = R = R = R = H , l u t e o l i n
2
4
(3.273) R ' = R = R 3 = M e , R = H
2
3
4
(3.274) R ' = H , R = M e , R = R = H
2
4
3
( 3 . 2 7 5 ) R ' = R = R = H , R = Me
2
3
4
(3.276) ' = R = R = H t R =Me, d i o s m e t i n
,
2
3
(3.277) K = R = l f . R
Mo

OR
(3.282)
(3.283)
(3.284)
(3.285)
(3.295)

:R = H , R = O H
R' =
2
3
R ' =R * = H , R = M e , R = O H
3
2
R ' = R = H , R = M e , R " "=OMe
r^ardenin
,
1
2
3
R =R =Me, R = H , R^=OMe, tangeritin
2
3
R ' = R = M e , R = H , R =OH

163.6

161.9

3 . .302

3 . ,303

3 . ,304

3 . .305

164.2

164.0

164.2

3 . ,308

3 . ,309

3 . ,310

3 . ,311

3 . 312

3 . 313

159.9

3 . ,307

159.6

162.8

162.2

162.1

3 . ,306

160.3

162.9

163.7

161.7

161.2

162.6

164.1

3. .298

3 . .301

3, .297

161.1

161.4

3, .296

3, .295

160.0

160.2

3. .300

3,.294

163.7

160.7

C-2

3 . .299

3,.293

3,.291

3..292

Str.No. Solv.

131,.9 158.5

182..0 156..5

182..4 156..9

182..1 156..5

182,.2 152..6
96.0

181,.7 161.,4

181..6 157..2

181..6 161..6

177,.9 119..5

177..7 120,.5

113 .2 176.,6 125.,1 124..7 133.9

95.,9 163.2

99..0 163.0

98..7 163.5

99..0 164.2

127..3 127.6

129..0 135.8

179..5 130..2 130..0 134.8

107 .8 175.,3 160.,0

103 .9

103 .6

103 .2

108 .1

108 .3

109 .5

94.9

158.4

99..2 157.3

131.,9 158.6

182..1 152,,7 131..3 157.2

96..2 158.7

99..2 157.4

110 .0 175..9 104..7 156..2

111 .9

112 .2

103 .6

102.7

112 .2 182..2 157..0

112 .2

96..0 158.5

182..4 158..8 111..8 159.1

177,.1 152..6 140..4 157.7

109 .0 182..1 156..6

103 .9

107.3

106 .0 176,.3 144..1 138..4 151.4

104 .4 183,.2 162..4 122,.4 164.7

105 .4 175,.8 153..8 139..6 157.3

103 .2 182,.0 152..5

C-10

C-l*

C-2'
150.1

C-3'

111.,7 121..9 113.1

156..9 105..3 123..7 110.5

151..5

108.,7

121..4 111.2

94,.3

114.9
1-9.3

128,.5

109.0

156..6

117,.9

132 .9 102.4 158..6

115

132

140 .6 153.1

103..0 105

103..8 156

153.4 141 .0 153.4 103..5 105

153.4 141 .0 153.4 103..5 105

153.1

102 .8 153.2

104..0 120..9 106.0 146.5

157..4 104..8 125..9 104.8 153.2

157..5

156.,1 123..0 116..2 142.5

146.3 149 .4 146.2 142..5 103

150 .1 111.3 123..9 32

141 .4 153.2 104..8 133

137 .9 146.5

106.,0 133
161..3 120..8 139..7 104.3 148.0 164.0 148.0 104..3 134

152..8 124..9 126..9 103.5

123..8 126..8 103.5

116..6 126.0 103.0

141..0 123..8 125..4 141.0 155.1

92..1 158.,7 109..7 125..0 110.3 148.0

94.2

94,.1

93,.9

120,.3

122

122

150..0 104..2 108..3 157.0 106.7 132 .2 106.7 157,.0 123

120,.0 153..1

117,.1

149,.3

158,.3
133 .1 104.6 158..3

133 .0 104.5

120

131,129

103,120

103,127

130

103

103

148.0 150 .7 115.7 120,.3 132

104.6

124..5

148 . 8 116.6 121.,0

151.0 119 .2 120.1

104.5

128,,5

151 .9 112.8 119..6

161 .4 114.9

121,.2

118,.4

118,.0

103

C-6' Ref.

152..2 105..1 122..8 109.4 149.0 152 .0 111.7 120..1

127,.8 150..8 103..9 109..3 156.9

91,.6

104..1 110..2 158.3

103..8 110..3 158.3

152..4 104..1 121..5 110.2

149..9

127,.8 150..6

128,.4 149..0 103..9 125.. 4 146.2

148 .9 115.9

148.8 151 .3 116.3

145.5

94,.0 162..7 104..2 122.. 5 111.3 151.5

96 . 3 154..5

128,.6

C-5'

147 .9 115.8 119,.7

C-4'

152..0 111..9 122..8 105.0 146.7 151 .2 112.9

151..4 111..9 121..9 110.1

C-9

134,.4 148..1 116..7 122..0 128.5

94,.1

96,.9

91,.2

96,.9

C-6

105 .7 175..6 153..7 139,.7 157.3

C-5

C-8

C-4

C-7

C-3

136

137

OR

OMe
,OR^

OH

R 0

HO

MeO
OR
(3.286)
(3.287)
(3.288)
(3.289)
(3.290)
(3.291)
(3.292)
(3.293)
(3.296)
(3.301)
(3.302)

1
2

R R = R = R =H n e p e t i n
3
2
R' R =R^=H,R =Me cirsilol
2
3
R' R =R =H,R =Me jacesiolin
2
3
HA R = R = M e c i r s i l i n e o l
R'=R
2
3
4
R = R = R " * = M e fR = H
2
R ' = R = R 3 = M e tB - H
3
2
R ' = R = H , R = R =Me e u p a t o r i n
2
3
R R = M e , R 4= R

R
2
3
=
R
=
R = eM
R
sinensetjn
2
3
R =R =H,R =Me
2
3
H , R = R = R =Me

R 0

OH
(3.294)

complavin A
OMe

(3.297)

canniflavone-2
(canniflavin A)

(3.303)
(3.304)
(3.327)

R'=R =H,R =Me

2
3
R'=Me,R =R =H
2
3
R'=H,R =OH,R =Me

R'O

(3.298)
(3.299)
(3.300)

R'=R =H,R =Me,R =0H

wightin
2
3
R ' = R = R = H , R =OMe
2
3
R ' = R = M e , R = H , R =OMe

OMe

OMe
OMe

OMe
MeO

OMe

OMe

v ^ ^

OH

(3.313)
OMe
(3.312)

162 1 114 .0 175 .2

163 2

3.319

3.320

3.321

3.322

143.2

143.2

146.0

142.9

163 6

3.324

3.325

3.326

182 .7 150.0

182 .8 152.5

161. 1 112 6

161. 0 112 8

3.331

3.332

3.333

3.334

3.335

160, 7 112 6

155.2

182 .8 152.9

176 .9

151.9

162. 0 112 0 182 .9

157. 4 115 2

154.7

153.6

177.2

159 1 112 5

183 .1

109 5

100 4 177 .2 151.5

3.330

161. 9

156.6

182 .0 152.5

111 8 182 .1

102 6

152.6

141.6

152.8

3.329

160. 6

175 .2

103 1 182 .1

111 5

182 .5

3.328

163 6

162. 0

3.326

3.327

159.4

162 4 107 5

152.5

182 .0 151.9

163 7 102 7 182 .5

163 4 102 5

3.323

104 0 183 .0 153.2

3.322

102 7 182 .0 145.1

163.1

144.0

182 .0 144.7

160 7 106 8 176 .2

105 9

175 .5

3.318

114.4

162 1 111 .7 182 .2

162 0

3.316

C-5

183 .0 148.6

3.317

162 .0 108.8

161 8 111 .3 182 .2

C-4

C-3

3.314

C-2

3.315

Str.No. Solv.

152.2

147.9

152.7

C-7

152.0

150.7

132 6

132 5

130 0

140 0

132 4

158.8

158.8

158.6

C-3'

C-4'
113 3 115

102 1 158 1 103

150.1

C-6' Ref.

103

114.6 119 3 109 .3 148. 9 152.0 111 9 122 5 103

114 7 119 8 109 .7 149. 5 152.3 112 5 123 7 103

114 4 110 0 157 .8 104. 1 132.3 104 1 157 8 103

114 4 108 6 156 .4 106. 1 131.8 102 1 158.2

118 9 108 6 156 .4 105. 1 138.2 101 9 158 1 103

118 8 108 6 156 .4 106. 1 132.2

C-5'

109 5 148. 0 150.5

115 4 119 9 128

152 5

103 9 120 4 104 .3 148.2 139.8 148.2

104 3 132

88 8 152 9 142
90 7 151 0 142
90 7 152 5 142

106 3 106 3 154 .2 132. 4 154.8

106 3 109 0 153 .0 132. 9 154.9
106 4 108 5 153 .1 133 7 154.5

90 .7 152 9
151 0
152 5

92 .2
94 .9

96 .2

92 4 152 6 140

105 9 106 7 154 .2 136. 0 156.6

147.6 106 6 140

91 0 152 6 141,142
112 5 120. 2 147 0 145. 7 149.5
112 8 109 0 153 .9 136. 0 155.6

151 9

152 5

143 9 106 7 137

143 7 102 7 138
106 2 119. 6 141 5 139. 8 149.1

149.6

142 7 146 3 115

152 6

96 .8

96 .2

90 .7 153 0

125 9 107 3 144.2

103 9 115 1 150 .7 111. 4 120.1

148 4 114.9

148 5

94 .4 152 4 104 0 120.4 104 .2 148. 1 139.7 148 1 104 2 137

94 .5

99 .0

110 5 123 0 141 .2 119. 1 141.2 149 3 113 2 136

106 1 121 6 109 9 148. 0 150.8 115. 9 120 2 128

105 7 120.9

107.2 121 0 108 .0 149. 8 149.7 115 0 121 0 135

153 8

143 0

147 6

145 9

105 1 107 1 152 .2 104. 8 152.2 141 9 112 9 136

138 .1

157.7

C-2*

91 .7 153 3

134 .1

132 .1

126 .3

147.6

159.0

148.2

147 3

C-l'

106 3 118 3 150 .1 117.0 120.9

C-10

148 0
127 .7 148 1 115 7 121 4 109 .7 150. 5 147.8 115 7 119 9 103

138 .1

132 .3

137 .3

157.5
159.1

148.2

147 9

145 6

C-9

137 .4 147 3

132 .2

133 .9

132 .8

C-8

127 .9

157.3

140 4 157.7

132 7

138 3

99 3

131 3

131 4 157.8

157.9

158.7

132 1
139 3

141.8

144.1

147.3

150.5

132 8

135 3

131 0

131 3

138 1 151.4

135 6

137 2

137 4 150.7

135 5

133 9

135 9

C-6

138

139

OR
3

(3.314) R ' = R = R = H , R | = O M e , R =0H

2
3
( 3 . 3 2 4 ) R ' = R = R = H , R = O H , R =OMe
arcapillin
.
^
3
2
( 3 . 3 2 5 ) R ' = R = A c , R = H , R = O A c , R =i

(3.315) R ' = R = R = H
3
2
( 3 . 3 1 6 ) R ' = R = H , R = M e s k u l l c a p f l a v o n e I]
2
3
(3.317) R ' = R = M e , R = H
2
3
(3.318) R ' = R = R = M e

OMe

OR

(3.320)
(3.321)
(3.322)
(3.323)

5-demethylnobiletin
2
3
4
R'=R =R =R =Me nobiletin
1
3
4
2
R =R =R =H, R =Me
sudachitin or majoranin
4
2
3
R'=R =H,R =R =Me
7-methylsudachitin
2
4
3
R ' = R = R =H, R =Me

(3.334)

(3.337)

R ' = R

(3.338)

R'=H,R =0Me

(3.339)

= H , R

=R5=Me,agehoustin'B

= R
2

= R
3

=Me

R'=R =H,R =R =R =Me

OMe

OMe
2

R'=R =H,R =R^=R^=Me

(3.335)

R'=OMe,R =H

R'=R =R =R4

(3.333)

OMe

OR

(3.332)

(3.336)

(3.326) R ' = R = R = R = H , R = M e
2
3
( 3 . 3 2 9 ) R ' = R = H 4R = R = M e t R = O M e
2
3
( 3 . 3 3 0 ) R ' = R = R =R = M e , R = O M e

R'=OMe,R =H
2

R'=H,R =OMe

165..4 104.0

3.,344

159..0 119.4

158..5 120.1

158.,5 120.9

158.,9 119.4

158.,2 121.8

159.,5 121.5

MC

MC

MC

3.347

3.348

3.348

3.349

3.350

3.350

3.351

3.352

3.353

3.354

3.355

3.356

3.357

121.6

183.3

181.7

119.7

159.2

155.2

155.8

155.8

155.8

183.3

152.1

152.2

151.9

152.9

156.8

155.0

151.2

161.1

161.1

126.6

159.6

152.1

183.3

138.1

138.0

137.9

92.5

97.5

98.5

98.5

98.5

99.1

99.9

99.9

98.9

99.6

98.5

97.9

98.9

100.5

105.5

114.4

99.7

C-9

C-10

C-l*

C-2'

C-3'

156,.1

156,.1

148..3

108,.9 108..9 140 .7 148.9

161,.3

160,.8

160,.9

160,.9

160,.6

163,.6

163,.6

162,.0

112..9 148.9

140 .7 140

140

C-6' Ref.

155..7

92..8 153 .0 140

148..3 114,.7 101..9 141,.0 149.1

92.,4 152 .9 140

115..0 149.,1 141 .0 140

136.2 155..8

114,.7 119..8 147.4 144.8 149..5 147.,8 106 .1 140

109..2 109..2 154 .2 136.3

157..6

115..5 111..9 160,.0 102.9

156.,1 106.,5 130 .8 87

163..4 116.,3 125 .0 143

156.,6 107.,0 131 .1 87

113 .2 161,.0 104.4 162.,4 108.,0 132 .3 144,153

113.,1 153,.9 104.1

107.,0 131 .3 144,146

162.,0 107.1

131 .4 149

106.,8 160.,3 103. 1

162.,0 108.,2 132,.2 151

111. 4 156,.3 102.6 160.,8 106.,8 131 .2 157

107.,9 160.,8 105.,6 113. 3 161,.2 103.6

108.,0 160.,9 105.,7 113. 4 161,.3 103.7 162.,2 108.,3 132,.3 152,153

108.,0 160.,8 105.,7 113.,4 161,.1 103.7 162.,1 108.,3 132 .3 150,151

140.,6 160.,6 100.,8 111. 2 156,.7 103.1

10 4.
,4 161.,6 101 ,
.3 114.,0 158,.2 112.4 162.,4 108.,8 138 .8 144,148

104.,5 161.,4 101.,4 114.,2 151,.1 112.3 162.,4 109.,0 130 .7 144

104.,4 160.,7 100.,5 110.,9 156,.7 103.0 161.

162..7 108.,1 132 .3 144

160..3 108.,1 132 .1 144

160.,3 103..4 111.,3 156,.5 102.7 161..2 106.,7 131 .2 145,159

107,.9 162.,0 104.1

105..5

105..1

151..8 104.4 110.,9 160 .6 103.0

106..9 162.,9

98..9

98..0 155..0 103..6 111..3 160,.3 102.8 156.,5 106.,7 130 .9 87

101..9

94,.7 158..8 105..3 123..2 128,.8 137.2

138,.4 148..2 114..9 116..9 143,.4 147.8 150..3 146.,8 143 .4 103

138,.1

C-5'

114..8 149..1 141 .0

C-4'

106,.0 119..7 147 .2 145.4 149..2 147.4 106 .0 140

138,.0 148..2 115..0 109..1 154.1

137,.9

130,.8 156,.2

130,.5

130,.5

96,.4 152,.7 112,.8 102,.0 141 .0 149.1

C-8

162 .7 105.,6 162.,7 101..3 112.,7 158,.5 104.5

162 .6

161 .7

162 .9

161 .7

161 .6

162 .1

164 .9

151 .7

151 .3

151 .0

151 .5

156 .3

156 .3

156.2

92.6

157.7

92.6

C-7

140.4

C-6

144. 4 138.4

144.1

143.8

144.1

152.8

151.8

152.4

155.3

C-5

182.2

181.7

181.7

181.8

183.1

183.6

181.8

183.3

181.7

181.7

176.2

183.0

176.0

156.,7 121.5

157. 3 121.6

156. 7 121.7

158. 8

159.,8 117.1

159.,7 117.2

158.,6 120.2

160..3 121.2

3.345

3.346

157,.9 114.9

176.9

158,.1 114.7

3.,342

3.,343

177.7

177.3

112.1

177.8

177.7

177.1

176.9

C-4

158,.1 115.3

159.0

156,.3 115.5

3,,339

158,.0 112.3

3.,338

114.8

157,.4 114.8

158,.9

C-3

3.,341

3.,337

C-2

3.,340

3.,336

Str.No. Solv.

140

141

OME

OH
3

(3.340) R ' = R = O M e , R = H
(3.344)
3
2
(3.341) R ' = R = O M e , R = H a g e h o u s t i n A
2
3
(3.342) R ' = H fR = R = 0 M e
2
3
(3.343) R ' = R = R = O M e

kuwanon S

(3.345)

(3.347) R ' = R = R = H , c u d r a f l a v o n e
( 3 . 3 6 9 ) R ' = H , 2R 2 =3 R 3 = M e
(3.370) R ' = R = R = M e

(3.350)

morusin

(3.346)
(3.348)
(3.361)

R ' = C H 2C H = C ( M e ) 2, R = R = H , m u l b e r r i n
3
2
R ' = R = H t R = C H 2C H = C ( M e ) 2 Kuwanon C
2
3
R ' = R = H , R = C H 2C H = C ( M e ) 2
kuwanon

(3.349)

tetrahydrokuwanon

(3.351)

R-\.,

(3.352)

R=OH

raorusin

hydroperoxide

142

(3.353)

(3.356)

(3.359)

morusinol

(3.354)

R = C H 2C H = C ( M e ) 2

(3.355)

R=H moracenin

moracenin A

moracenin C

moracenin D

(3.357)

R=H,kuwanon G

(3.358)

R = C H 2C H = C ( M e ) 2, k u w a n o n

143

(3.360)

kuwanon

OH

(3.362) kuwanon
3
R
4
OR

OH
(3.366)
(3.363)

R ' = R 4 = H . R = C H 2C H = C ( M 6 ) 2, R = 0 H
2

(3.364) R ' =R =R4 = H tR = O H , 5 - h y d r o x y

cudraflavonp A
2
4
(3.365 ) R ' = R = R 3 = R = H c u d r a f l a v o n e A
1

( 3 . 3 6 8 ) R =R = M e , R = R = H

Protogenkwanone

161 .6

161 .0 120,.3 181,.8 161,.5

152 .8

156 .8 109,.8 178,.7 156,.9 105.,7 159,.4

3.361

3.362

3.363

3.364

155,.4
98,.0 163,.7

98,.3 164,.0

155 .7 107.2

158,.7 109..3 172,.7 158..4

3.368

166. 2

93 .2

C-4'

C-5'

106,160

147,159

69. 8 148..1 129.5 185. 0 129. 5 148.,1 169

118..2 131.,4 126 .2 129. 0 131..4 129..0 126,.2 164

117.7 131.,6 126 .2 129. 1 131..1 129..1 126 .2 166
117..7 131.,5 126 .5 129. 0 131..5 129..0 126 .5 166
119..5 132.,0 126 .9 129. 4 132..0 129..4 126 .9 163
117..7 132.,2 126 .8 129. 4 131..6 129..4 126 .8 164

153.9
153.9
153.0

111,.5

162,.6 107.,7 177..4 129.,1 111.,8 164..8 111,.5

114,.5

162,. 1 106..9 177..1 127.,4 112 .8

. 163..5

161,.6 106.,6 176..3 127.,1 112.,7 163..0 114,.8 152.6

162,.1 106..4 176.,6 126.,4 111.,4 164..2 113,.7 153.7

163,.4 107..6 177.,8 129.,4 109.,2 164..2 109..3 153.9

, 110..9
163..2 108..0 177..9 126.,3 117.,7 160 .9

C+D

3.373

3.374

3.375

3.375

3.376

3.376

3.377

3.378

3.379

119..2 132.,0 126 .7 129. 4 132..0 129..4 126,.7 163

118,.7 131.,8 126 .2 129. 0 131..4 129..0 126,.2 165

162,.3 108,.1 177..8 129.,4 109.,3 163..3 110,.0 153.7

162,.9 107,.7 177..5

128.,7 111.,8 164..6

154.8

126,.1 163

117,.8 131.,8 126 .1 128. 9 131..4 128.9

118,.5 131.,7 126 .2 128. 7 131..5 128..7 126 .2 166

118,.4 131.,7 126 .6 129. 1 131,.8 129..1 126,.6 163

129..8 109..3 167.1

113,.0 158.1

163,.9 105..8 178..5

161..6 107..2 177..5 128..0 109.,3 163..0 114,.2 158.0

162,.4 107..3 176..8 130..0 109..0 165..9 112,.0 153.7

118,.7 131., 2 126 .1 129. 0 131..7 129..0 126,.1 163

158..9 104.. 6 131,.6 162

98. 7 159..1 104,.6 131 .3 162

112,.6 115.,4 158 .4 1005

104,.9 114,,8 160..5

3.372

98,.8 155.3

3.371

157..9 112..1 162..4

157,.5 123..2 176..5

112.6 125 .4 109.2 158..5 103..0 158,.5 162

158.2

113,.0 112.,1 105 .8 144. 8 151..8 101..3 150,.6 162

106. 1

105,.0 108..5 128 .7 110. 3 155..7 103..8 157,.8 162

105,.7 107..2 109 .6 141. 0 151..8 105..0 152 .1 162

108,.3 108..9 114 .8 137. 5 150..3 105..6 140 .8 161

103,.6 112..9 154 .5 116. 6 158..0 105,.8 128 .2 143,72

103,.7 111..8 153 .3 115. 8 157,.8 106,.9 127 .5 143

103,.3 111..9 156 .1 103. 3 158,.3 107,.0 130 .8 147

104.5 112..4 160 .2 102. 6 161,.0 107,.1 131 .2

129 .5

C-6' Ref.

94,.7 156.5

C-3'

101,.3 153.3

100,.8 154.0

93. 0 158.3

95,.0 155.8

95,.4 156.7

C-2'

3.369

121..1 182..3 157..3 104..8 162..6

157.4
152.2

C-l*

103 .9 111..6 156 .4 102.,7 160,.9 106.9

C-10

3.370

165..1

173..5 157..9 113.,0 158.7

98. 9

155,.6 104..9 163,.5

162. 6

3.367

182. 9

158 .6 106,.5 177.7

168.,3 107. 7

3.365

159.7

160.0

160.3

C-9

93 .4 157.9

98,.0 160,.4 106 .8

177,.7 153..6 107,.0 155,.7 104,.6

3.366

104.4

120,.2 181,.8 161,.5

120,.0 181 .9

106 .9

C-8

160 .0 107 .0

158 .5

97,.5

161,.6

C-7

154,.9

97,,3

C-6

3.360

156 .3 121,.5 182,.5

159 .3 119,.8 181,.8 155,.3

C-5

MC

C-4

D+M

C-3

3.359

C-2

3.358

Str.No. Solv.

144

145

R2

(3.371) R=Ac g l a b r a t e p h r i n
(3.372) R=H g l a b r a t e p h r i n o l

(3.373)

apollinine

semiglabrin
(3.374) R ' = * - H , R = A c
2
(3.375) R ' = * - H , R = A c p s e u d o semiglabrin
2
(3.376) R ' = / e - H tR = H s e m i g l a b r i n o l
2
(3.377) R ' = - H , R = H p s e u d o s e m i g l a b r i n o l

R'

2
(3.379) R ' = R = H i s o s e m i g l a b r i n o n e
2
tachrosin
(3.380) R ' = O M e , R = M e
2
(3.381) R ' = H , R = M e
tephroglabrin

(3.382) R ' = R = H l a n c e o l a t i n
2
(3.383) R ' = H . R = 0 M e kanjone
1
2
(3.384) R = O M e , R = H

OR
KSO,O

OMe
(3.385)

pinnatin

(3.386)
(3.387)
(3.388)
(3.389)

R'=R =H
2
R=OH,R =H
2
R ' = H t R = S 0 3K
2
R ' = 0 H , R = S 0 3K

164.6

164.0

3.388

3.389

165.7

165.8

3.387

107.6

161.0

3.386

102.3

103.2

3.291 56.0, 60.7, 61.6;

3.292 55.8, 56.3, 60.1;

3.286 60.1;

3.280 56.1, 60.2;

3.285 55.8, 61.8, 62.0;

3.278 55.9;

3.268 55 .5,

3.293 56.3, 60 .8,

3.287 56.3, 59 .9;

3.281 56.4, 60 .7;

3.267 55.5, 61.0;

3.261 55.9, 56 .3;

3. 256

3.250 59 .9;
3.255 55.7, 56.7, 60.6;

3.249 55.7, 56.2, 60.6, 61.4;

3.260 56.0, 56.5, 61.0;

3. 230
3.242 55.8, 60 .3;

3.229 61.7;

3.221 56.1, 60.3, 61 .3;

3.241 55.8, 60.2, 60.9;

3.266 55.1, 56.8, 61.2;

3 .277 55.7, 55.9;

3.284 55.3, 60 .2, 61.1 ;

3.290 56.2, 60.1, 61.6;

3.276 55.8;

3.283 62.4;

3.274 55.9;

3.289 56.,0, 56.4;

3 .271 55.9;

3.220 60.0;

3.210 56.0;

3.197 53.0, 56.0; 3.198 55.6,

3.206 55.9, 60.2;

3.228 56.6, 61.1;

3.254 56.8, 57.2;

3.259 55.9, 60.9;

3,.265 61.1;

3.258 55.9, 61 .0;

3.282 60. 2, 61.2;

61.8;

3.238 56.1;

3.247 60.3, 61.3;

3.253 55 .9, 60.5, 61.3;

3.264 56.8, 57.1;

3.257 55.9, 60.3;

3.263 61.0;

56.1, 60. 6;

3.262 60. 0;

3.252 56.3, 59.9;

3.251 56. 2, 59.9;

3.246 61 .4;

3,.237 55.5;

3.215 55.0;

3.205 55.7, 55.8;

3.226 56.5, 61.6;

3,.214 55.4, 56.2;

3.225 55. 9, 61.0;

3.234 55.1, 55.5, 55.8;

3.245 56.1, 59.4;

3 .231 56.3;

3.224 56.1, 60.6;

3.243 55..0, 55.7;

56.3;

3.223 56. 1, 60.6;

3.204 55.4;

3.189 55.1;

3.202 55.4;

3.213 55.8;

3.201 55.5;

3.212 55.1, 55.2;

3.199 55.8, 60.8;

3.211 55. 8;

56.0;

3.196 55.4;

181..9 160..9
3.195 56.7;

168
145..0 121.7 117..0

105..9 125 .8 114,.6 149.9

156.4

104..3 159..6

182..8 161..3

3.188 55.2;

168
129..5
157..0 121.1

106..8 125 .3 129,.5 121.1

97..6

120..6 168

151..8 116.1

106..0 120 .6 110..9 147.5

156..5

99..0 160.0

99..3
98.2

103..6 159..4

182..9 161..1

181..7 160..8 102.,6 159..2

103.5

101.2
160..0

129..4 168

162..9 117.2

106..9 121 . 1 129,.4 117.2

157.,1

105.,1

125,.9

131..1 128.8

153..4 112..6 131 .3 125..9 128.8

95..2

157..8

117.0

178..1 155..3

Other signals: OMe: 3.176 55.5;

167

91.,8 158..0 111..0 151..8 110..0 131 .2 125..7 128.3

177..7 158.0

109.4

3.385

125..7 167

131..2 128.3

160.0

3.384

125.,6 167

131..0 128.7

143,,9 147..8 116..5

116..9 150..5
149..8 119..6 131 .4 125..6 128.7

99,.6

109.,8 158..1

164

C-6' Ref.

167

C-5'

125.,9

C-4'

131..4 128.9

177..5

107.7

C-3'

119..1 131 .4 125..9 128.9

177..8 161..3

106.9

161.8

3.383

107.6

C-2'

128.,9 163

C-l'
126 ,2
.

C-10
131.,1 128.8

C-9

131,,7 129.2

C-8
98..4 156.,8 109..1 131 .8 126.,2 128.8

C-7

109..7 155.,1 118..6 132 .6 126..9 129.2

C-6
91.,8 161..5

C-5

178..4 127..4 109.,5 164.0

C-4

121..5

162.3

108.8

C-3

177.9

161.8

3.381

3. 382

3.380

161.1

C-2

Str.No. Solv.

146

18.4;

3. 363 121 . 1 , 131 . 1 , 25 . 2,

18. 1 ;

3.344 28.9, 122.9,

131.8,

71.9, 27.6, 25.2.

3.352 22.7, 86.0, 82.9, 25.9, 20.3.

3.351 25.5, 90. 9,

38.5,

124.0,

3"-dimethyl dihy dropyrano)-benzoyl) -CH-( 2 , 4-dihydroxy phenyl) :

3.356

3 8,6,

134.1 , 23.0,

( 2, 4-dihydroxy phenyl)-CH-( 2 ,4-dihy droxybenzoyl) :

29.8, 121.1, 155.9, 102.7, 155.9, 106.9,

161.6, 106.9, 131.3.

39.2,

2 , 4-dihy droxybenzoyl) :

3.358

38.8, 123.4,

132.9, 22.6,

131.3, 45.7, 114.0, 162.1, 113.7, 21.4, 122.4, 130.5, 22.5, 17.5,

-CH-CH=C( Me )CH2CH( 2,4-dihydroxy phenyl)-CH-( 3-isopreny 1,

132.7.

133.2, 22.0, 37.1, 37.6, 121.5, 155.8, 102.0, 155.8, 107.0, 128.8, 47.0, 208.8, 114.5, 164.0, 102.8, 164.7, 107.3,

3.359 37.6, 122.9,

3.357 22.9, 123.2, 132.8, 25.5, 38.3, 22.9,

120.7, 155.8, 102.0, 155.8, 106.8, 132.4, 45.8, 208.1, 114.0, 164.2, 102.6, 164.2, 107.2, 130.8;

-CH-CH=C(Me)CH 2CH

122.4, 156.7, 103.6, 156.6, 107.9, 129.2.

124.0, 134.1, 23.0, 37.9, 38.6, 209.9, 114.5, 161.1, 109.0, 16.7, 32.1, 76.5, 26.6, 26.8, 163.1, 109.2, 130.3, 47.7 ,

CH-CH=C(Me)-CH2-CH(2-hydroxy , 3 , 4-( 3

3.366
3.345 24. 1 ,

134.1, 38.0, 35.8, 209.8, 115.5, 165.1, -, 165.7, 108.3, 133.8, 47.9, 122.4, 156.7, 103.0, 156.7, 108.3, 130.3.

CH-CH=C( Me )-CH2-CH( 2,4-dihydroxy-2-prenyl-benzoyl)-CH-( 2 , 4-dihydroxy phenyl) :

CH 2CH(0)C(Me) 2OOH:

3.354

27.5, 126.6, 129.9, 25.8, 17.8;

3.370 24.7, 122.3, 130.9, 25.5, 17.5.

3.349 20.8, 38.9, 28.3, 22.8x2, 23.6, 38.1, 28.3, 22.6x2.

CH 2CH(0)C(Me) 2 OH:

CH^CH 2CH(Me) 2:

16.3, 40. 5,

3.369 24.1, 12.6, 131.8, 25.6, 17.5;

3.361 23.6, 121.4, 130.0, 25.4, 17.2,

3.363 20.5, 121.8, 131.0, 25.2, 17.6;

3.360 23.5, 122.1, 131.4, 25.2, 17.3;

3.358 23.8, 121.9, 131.3, 25.5,

3.354 24.5, 122.4, 132.9, 25.8, 17.7, 22.0, 122.7, 132.5, 25.8,

3.357 23.5, 121.8, 131.2, 25.4, 17.3;

122.0, 133.9, 15.6, 39.2, 26.1, 124.0, 130.3, 25.3, 17.4.

CH 2CH=C(Me)CH 2CH 2CH=C(Me) 2:

122.1, 131.7, 25.5, 17.5;

24.4,

138.3,

3.375

3.348 23.5, 121.7,

3.365 69.2, 121 .3,

3.374 170.0, 20.8;

3.347 23.9, 121.6, 131.1, 25.5, 17.4;

3.362 24.1, 121.3, 129.8, 25.3, 17.5;

21.4, 122.4, 130.5, 22.5, 17.5;

123.0, 131.1, 25.5, 17.7;

17.5,

3.356 24.5, 122.4, 132.8, 25.7, 17.7;

22.2,

17.9;

131.2, 25.4, 17.3, 21.1, 122.1, 130.7, 25.4, 17.3;

138.1 , 25.6, 18.4;

3.371 168.6, 19.7;

3.368 71.0, 122.5, 138.4, 25.7, 18.6

3.364 69.5, 121 .8,

3.229 168.4, 20.5;

3.346 23.9, 122.2, 130.9, 25.6, 17.5;

3.367 70.2, 121.4, 138.7, 25.7, 18.6;

CH 2CH=C(Me) 2:

25.5,

C H R : C H C ( M e ) 2:

3.226 168.5, 20.4;

3.375 169.8, 20.3.

3.211 169.7, 21.1;

169.8, 20.0;

OCOMe:

147

3.297 56.8;

56.3,

59.9;

3.385 61.6.

3.278 128.0, 126.8, 124.9, 121.9.

3.189 128.4, 119.9, 155.5, 107.1;

3.177 22.4; 3.195 15.6;

CH 2CH 2C(Me) 2OH:

3.359 20.0, 41.9, 70.2, 28.1, 28.2.

5.230 114.7, 143.7, 70.4, 30.2x2.

3.353 28.0, 42.1, 63.3, 29.0x2;

CH=CH C(Me) 2OH:

3.381

3.367 116.3, 130.6,

3.364 115.6, 128.8,

3.370 116.3, 130.2, 77.2, 28.1x2

3.366 115.5, 128.4, 78.0, 28.2x2;

3.369 115.7, 127.7, 77.0, 28.1x2;

3.365 114.7, 125.6, 77.9, 27.8, 27.9;

3.368 116.4, 131.7, 78.3, 28.3x2;

3.380 56.3;

3.343 61.6, 62.2;

3.352 115.4, 127.6, 78.3, 28.1x2;

3.363 114.8, 128.4, 77.4, 27.5, 27.4;

3.354 114.3, 127.6, 78.0, 27.7x2.

3.360 114.7, 128.3, 77.4, 28.0, 27.8;

28.1, 28.2;

77.5, 28.0x2;

78.3,

CH=CH C(Me) 2:

3.353 114.5, 127.9, 78.4, 28.0x2;

62.2:

3.200 127.6, 126.6, 124.7,

3.373 56.5;

3.202 129.0, 118.1, 158.4, 101.5.

3.347 114.3, 127.1, 7.8, 27.7x2;

3.196 8.1.

CH=CH C(Me) 2: 3.222 114.2, 128.8, 77.8, 27.7x2;

Me: 3.175 20.1;

-C(OMe)=CH-CH=CH-: 3.201 155.1 , 107.1, 119. 1 , 113.8.

-CH=CH-C(OMe)=CH-:

3.370 55.4x2, 62.6;

3.342 56.7, 61.7, 62.0, 62.2;

3.194 128.4, 125.7, 126.3, 126.9;

3.369 55.4, 55.5;

-CH=C(OMe)-CH=CH-: 3.188 106.0, 159.8, 118.0, 129.0.

121.7,

3.384 56.6;

3.368 55.9, 63.0;

3.341 56.1, 61.0, 61.8, 62.1;

3.187 172.1, 129.1, 126.5, 128.0;

3.383 56.0;

-CH=CH-CH=CH-:

56.5;

3.367 56.0, 56.5, 62.7;

3.340 56.2, 61.3, 61.7, 61.8, 62.2;

3.336 56.3, 56.8, 61.6, 61.7,

3.339 56.2, 56.3, 56.7, 61.0, 61.4, 61.7;

3.335 56.2, 56.3, 60.9, 61.2;

3.338 56.0, 56.1, 56.4, 61.0, 61.1, 61.2;

3.334 56.3, 56.4, 56.6, 60.8, 61.3;

3.337 56.1, 56.4, 61.2, 61.4;

61.3;

3.333 56.0, 56.3, 60.8,

3.320 56.3, 56.6,

3.326

3.321 56.0, 59.8, 60.0;

3.325 55.5, 56.8, 61.0;

3.332 56.0, 60.9, 61.3, 61.4, 62.0;

3.312

3.316 55.8, 60.2, 61.4;

3.329 56.4, 60.8, 61.1;

3.324 56.5, 57.2, 60.1;

3.328 56.7, 61.6, 61.8, 62.0, 62.2;

3.331 56.1, 56.4, 60.9, 61.2, 61.7;

3.327 60.6, 61.0;

61.3, 61.5, 62.2;

3.323 55.8, 60.9, 61.8;

3.320 56.3, 61.9, 62.3;

3.315 55.7, 60.7, 61.5;

3.319 55.5, 60.2, 61.4;

3.314 60.6, 61.5, 62.0;

3.318 55.7, 61.3, 61.5;

3.313 60.1, 60.6;

3.322 55.3, 60.0, 61.0, 61.3;

3.317 55.7, 61.4;

55.4, 55.8, 55.9;

3.302 55.7, 55.9,

3.308 56.3, 60.9;

3.301 55.9, 59.9;

3.307 56.3, 60.9;

3.300 56.2, 56.5, 61.0;

3.305 55.1, 55.7, 56.0, 60.1;

3.299 56.1, 60.9;

3.303 56.0, 61.0, 56.5;

3.295 62.4;

56.4, 60.0;

61.8;

148

149
A
tional
and

further

heterocyclic

C-6'

absorb
and

unique

of

the

ring

formed

B-ring.

at S 7 0 . 1 0 . 9

C-6'

category

carbon

compounds

as

it

at S 1 5 1 . 4 0 . 8

3-prenylatedflavones

in

between

carbon

corresponding

oxyaryl

absorbs

The

of

A
in

of

forming

at

(3.365)

158.20.4
and

its

an

in

prenyl

chain
ring

substituent

4'-oxysubstituted

ether

compounds

addi-

additional

isoprenyl

ppm

dimethyl

3'-oxysubstituted

C-3
the

to o x y m e t h i n e of t h e

absorbs

cudraflavone

methylene

resonances

possesses

as

(3.368)

while

3.364 and

3.367

(3.373),

tephro-

[162].
Several
glabrin

(3.381)

species

[164],

causes

ca.

shift
of

ca.

novel flavone derivatives

and

in
ppm

5 ppm

7-OMe

tachrosin

due

(3.380)

are

ppm

characteristic
ppm

(3.380),
in

the

to

Several

other

novel

semiglabrin

and

pseudosemiglabrinol

and

include

in a range

the

The
latin

of

(3.382),

intensity

at a r o u n d

furano

to

112.5

chemical

Barron
and

luteolin

due

to

para

signal

at

C-9 is

least

of

for

change

the

chemical

while

116.1

which
161.1

fused

as

is

ppm.

bifuran

ring

(3.376)

discussed

dioxygenated

at

tachrosin

ppm
at

158.3.

that

For

semiglabrinol

effects

and

s i g n a l at

case.

C-8

three

angular

3.384,

and

and

has

around

C-4

been

studied

in

to C - 1 0 i s

remains

Ibrahim

[168]

A l l of

C-7

absorbs

at

C-6,

C - 8 and

C-10

of

5 150 a n d

intense

flavone nucleus

(3.386-3.389).

which

related

and

and

upfield

(3.373)

but

i.e.

regarded

(3.375),

similar

subcategories

corresponding

to t h e

at
is

C-7

signal

(3.383)

(3.385)
two

of

exhibit
the

NMR s p e c t r a

these

shift

moiety

of

kanjone

of t h e

assignable

with

significant

carbonyl

appear

which

above

bifuran

methine

furanoflavone,

lanceo-

[164-166].

pinnatin

differentiated

8150
The

ppm

carbon-13

4",5")-flavone,
who

(3.377),

nature

data

C-8

conformational

respective

pseudosemiglabrin

appearance

108-113

to

Tephrosia

to

Apollinine

lactone

of a v a i l a b l e

compounds

(3.374),

its

carbonyl in the
[164]

but

compounds

for

from

linked

the

C-8.

8-substituted

reported

amount

is

by

at

indicative

isolated

unit

unusual

-unsaturated

g ,

been

large

with

substituent

are

apollinine

been

accompanied

isomeric

group

for

has

with

have
derived

along

bulky

the

carbonyl

C-2

as

C-8

f o r OL , - u n s a t u r a t e d

analogy

such

of

C-6 probably

group

of

(3.380)

cyclopentenyl

shift

of

shift

204.6

techrosin

which

such as

as

it

least

these

upfield

intense

mono

carry

at

furano-(6,7:

The

et^ a K
on

by

around
and

sulfate

1.5-4.0

around
signal

furanoflavone
fusion o f

178

ppm.

group

ppm

basis

the

disulfate

(4.0-5.5

at

while

in linear

[166]

the

signal

furanoflavone

a b s o r b s at

position

absorb

112.5.

unaffected

identified

linear

Talapatra

furanof l a v ones

angular

almost

one

by

at

ppm)
lower

of

apigenin

C-7
and

the

position
ortho

field

and

position

150

relative
group
and

to

respective

also

exhibit

downfield

group

shifts

Murakami
which

at

wanone
is
the

to

C-4'

ing

and

in

is

to

due

and

ring A e x h i b i t

of

C-2

and

substituent
and

C-2

flavone

are

C-3
into

and

resonance

at

fully

ipso

sulphate

The

at

difference

of l a t e r .

absorbs

at

in

The

64.5.

almost

at

the

deshielded

(3.250).
a

The

6 69.8,

C-4' is

chara-

hydroxyl
71.3

and 6 209.3
chemical

The

the
ring

tetrahydroprotogenk-

bears

at

185.0

[169]

reduced

relatively
in

which

to a s i g n a l

resonance

3^218.

3-hydroxy

group

and

72.5

corresponds

shift

is

due

to

of h y d r o x y

methine

resonances

belong-

carbon

same positions

as in

flavones

the

FLAVONOLS

derivative

dramatically
flavone

moves

comparison

[168]

induced

by

with

the

skeleton.

upfield

of

affected
via

C-6, -3.2;

flavones.

by

The

the

17

The

chemical

introduction

C-3 shifts

ca.

and

C - 2 and

comparison

made
to

the

C shielding

ppm).

C - 3 are

133.5-151.2
as
C-3

C-2

flavone

of

downfield
ppm

ca.

in

shifts

the

ca.

for

unsubstituted

chemical

3-OH

32

ppm

going

from

usually

resonance

98]

infers

C - 3 , +31.4;
C - l ' , +0.5;
shifts

of

flavonol
the

shifts

C-4, -5.4;
C-2' /C-6',
the

C-5
-1.3;

aryl

carbon

displaying

signals

c a t e g o r i e s of f l a v o n o i d s .

quaternary
ppm.

[13,

18.0;

C-10,-2.7;

The

in both

data

(3.171)

( C-2, -

C-9, -4.7;

C - 4 ' , -1.7

between

substituents

exhibit resemblance

Both
readily

the

C-8, +0.2;

resonances

of

unsubstituted

3-OH

C - 3 / C - 5 ' , +0.5';

can

of

reported

or

( 3 . 3 6 5 ) , 175.4

giving rise
The

absorptions

are

C-4

(3.390)

usually

site

the

to f l a v o n o l .

-3.9;

the

hydroxyl

of

ring B .

These
C-2

recently

partially

C - l ' resonance

3.5

of

reflect

C-4'

shift

in tetrahydroprotogenkwanin

to

type

case.

therefore

with aromatic

have

having

of c o n j u g a t i o n i n c a s e

3.250,

of

upfield

carbons

coworker

at S 1 7 1 . 8

3.366

absence

his

apperance

quaternary

Sulphatation

therefore

para

in protogenkwanone

respective
in

and

flavonoids

the

absorption
of

in

ortho

and

to

compound.

behaviour,

3.7).

three

S168.3

(3.218)

cteristic

the

of

results

position

type

of

(see also section

identification

and

hydroxy

similar

oxy-olefinic tyne

Assignments
resonates
(Table

3.4)

at

of

C-2

and

lowerfield

C-3

resonances

5.0-13.0

ppm

in

[21,30,38,56,61,91,97,168-188].

151
Generally

the

while that

appearing

The
an

shift

the

substitution

of

the

3-OH group.

5-methoxyl

comparably
A

at

shift

give

A c y l a t i o n at
ring A carbons,
well

as

result

of

the

a
to

downfield

vations,

noted

for

C-3

ppm

and

of t h e

4.1

and

to
at
ihe

an

as

If

in

much

but

C-8

C-6

absorbs
e.g.

are

3.5

also

105.8

almost

ppm

C-3

al_.

[91],

0.9

cause
shift

unaffected

by

in

noted

in

at

C-8

ca.

causes
at

the

(3.412)

in kushenol

the

acyl

contrast

at

to

3-acety-

smaller
C-3

This

(-5.5
is

the

the

ppm)

probably
relative

3.403)

introduces
respectively.

above

C-2

3.424
4.7

effects

substituent,

to

of

and

whereas

addition

of

C-2 resonances

ppm

whereas
flavonols.

case

induces

shift

2.3

3.421

5 ppm

ppm

significnt

resonances

in

with

[91].

ppm).

C-3 and

obser-

in

quercetin-

respectively.

and

4.7

downfield

ppm

shift

shifts

for

for

rapid

in

2.2

appear

at

whereas

at

[183]

in

98.7

of

The
3.424

and

C-8

relative
with

2.6

C-6
the

to

and

94.9

and

C-8

C-8 is
[187].

resogroups
not

ppm

and

compound.

in

ppm

so

Substitu-

C-8 resonance

103.9

kushenol

methine

methoxyl

8-unsubstituted
and

98.5
and

and

assignment

deshielding
as

C-6

field

substituted

position

C (3.427)

among

lower

are

chemical

same

noted

(+10.4

(3.421)

ppm

is

upfield

flavonols,

3.2

172.41.4

or

case.

about
in

C-5 position

5-hydroxylated

3.424

indicative

derivatizaion

in

3.402)

of

is

to

(3-allylkaranjin;

in

and

C-8 positions

significant

tetrahydroxylatedflavonol
and

C-2

of t h e

ppm

difference

position

C - 6 and

at

at

respective

C - 6 and

the

still

at

For

and

and

karanjin,

ppm

shift

C-6 resonates

3.433,

3.421

electronegativity

et_

at

ppm

significant

5,7-dihydroxylated

both

tion

sensitive

absorption

C-4 resonance

shift

10.1

C-20 in the

resonances,
nance.

not

in flavones,

also

177.31.5

ether-3-O-acetate

3.7

In

resonance,

unsubstituted

of

Pomillio

C-4

C-2

downfield

remain

with

causes

downfield

shifts,

also

flavonols

substitution

5,7,3',4'-tetramethyl
upfield

C-3

does

slight

is

rise

increased

However,

position

to

and

downfield

Allyl

shifts

leads

the

carbonyl

C-3 (3-acetyl

but

large

hydrogen.

C-2

to

to C - 3 .

position

position

position

on

at

but

of

lated- 5-methoxylated flavonol such as

as

corresponds

resonance

of

C-5

Hence,

field

upfield

ppm

ppm. corresponds

[168],

group

low

further

C-2

chemical shift

of

140.0-151.2

oxysubstituent

chemical

an V - o x y s u b s t i t u e n t
The

the

the

The

at

133.5-140.0

of

of

ppm).

appearing

at

presence

upfield

(0.9-2.3

resonance

5,7,2',4'and

G (3.428)

at

98.5

[63]

with

3.4

135 .5

135 .9

136 .3

134 .6

141.2

146.0

147.7

146,1

147.2

156.1

147.0

147.5

3..394

3..395

3..396

3..397

3..398

3..399

3..400

3..401

3..402

3..403

3,.404

3..405

3..406

3..406

3..407

3..408

3,.409

3..410

138, .9

172, .8

137.2

175

129 .5
129 .3

115, .4
115. .3

148. .3
159.2
159, .0

147. .4
115 .4
115, .3

107.4
129.5
129.3

123. .6
121 .7
121, .6

118. .0
103. ,1
102, .9

152 .6
156, .2
160 .5

120. .8
93, .5

134. .7
163 .9

133, .9
98, .2

125. .1
160, .7

172 .5

175 .9

127.5

128, 6 130, .2

128, .5

127 .6

179

177 .0

135, .1

151, .7

176.1

105, .6

159, .2
115, .4
129.5

121, .7
103, .5
151 .4

93, .7

157. .1

130. .9

160. .6

176 .0

146 .6

178
129 .5
115. .4

91, .9

146, .6

177
129 .3

92. .1

164. .9
164. .9

97. .4
97. .3

160. .3

176 .0

144. .5

176
129 .4
115. .4
113. .9

159, .3
164, .9

115, .4
113.9

129.4
129.3

121, .6
123, .1

104.0
104.0

156 .1
160 .5

93. .4

163. .8

98. .2

156. .0

175 .7

30,31

122 .6
108.3

129. .8

127. .6

154 .4

93. .0

135 .6

38
189

128 .5
127. .6

130. .4
128. .1
128.3
128.5

130. .4
130. .6

119. .3
110. .5

146, .9

117. .5

162. .2

138 .2

128 .3
128. ,1

154. .4

146.8

173
173

127, .9
128.9

103. .2

144.8

173

127.3
128. ,3
128.9

129. ,5
131. .3

128.3
127.9

127.3

109. .7

131. .2
129. .1

116. .7
118. .4

146, .9
149, .6

116. .7
116. .9

157, .4

154. .6

176 .3

120. .9

173 .6

143 .1

154.5

137 .1

121, ,0

171 .0

154.2

109. .6
110. .5

120.9

172, .7

133 .5

139 .0

124. .4

124. .0

172 . 4

137, .8

157. .8

97
121, .5

112. ,2
150. ,7
148. ,7
112.3

123. .8

133. .0

97

121, .7
116. ,7
148. ,1

145. ,4

116.3

123. .4

121. .1

154, .3

117. .9

121, .5

155, .4

118, ,8

134. .5

125. .4

125. ,4

172
127.7

131, .1

106. .9

156.7

103. ,9

163. ,3

90. .1

154.6

128. ,6
130. ,1
128. ,6

127.7

173 .8

176 .4

126, .9

128. ,4
129. ,3

128. ,4

126.9

131. ,2

106. ,3

158, .2

92. ,8

163. ,9

95. .7

160. .2

171
170

128. ,5
130. ,8

128. ,5

129.4

132. ,3

104. .4

157.7

94. ,6

165. ,3

99. .1

129, .4

162. ,3

171
128, .2
128. 3

142

142

170

170

170,174

Ref.

131. ,7

128. ,3

128.2

155, .7

101. ,2

168. ,1

105, ,4

161. .7

131, .0

120. 7

132. ,1

112. ,0

157.5

118. ,6

124. ,4

118. 7

131. ,5

116. ,6

156, .1

118. .6

133. ,4

124. ,4

125. ,6

127. .4
130. .9

128. 4

129. ,3

128. ,4

127.4

118. ,7

155.4

131. ,7

128. 4

129. ,4

122. ,0

131. ,5

114, ,2

127.6
127. .3

128.5

129. ,9

C --6'

128.5

C - 5'

128. ,4

C - 4'

127.3

C - -3'

127.6

C-2'

155, .1

133. ,4

124.4

118. ,4

156. .5

100. ,2

114.5

126. ,1
124. ,8

156, .6

102. ,0

162, ,6
163. ,6

114. ,9

126. ,5

131. ,3

C - -1'

121. ,3

C - -10

115. ,2

151, .6

118. ,3

133. ,7

122. ,0

121. ,8

C --9

C - -8

C - -7

C - -6

C - -5

flavonols3

138, .1

137, .6

171 .2

176 .5

137, .9

138, .8

176 .6

173, .3

138, .9

154.5

144.5

145.3

146.1

147.1

146.1

147.5

3.,393

172, .3

172, .3

138, .8

144.4

138, .4

144.1

3..391

173, .0

139, .0

145.2

3..392

3..390

C--4

of

C--3

shifts

C-2

Str. No. Solv.

C a r b o n - 1 3 NMR c h e m i c a l

TABLE

152

153

R Q

( 3 . 3 9 0 ) R ' = R 2 = R3 = H
2
3
(3.391) R ' = 0 H , R = R = H
2
3
(3.392) R ' = O M e , R = R = H
2
3
(3.393) R ' = R = H , R = O H
2
3
(3.394) R ' = R = H , R = O M e
2
R
'
=
0
M
e
,
R
=Me.
(3.398)
3
R =H

(3.399)
(3.400)
(3.405)

OR

OR

(3.395)
(3.396)
(3.397)
(3.398)
(3.406)
(3.407)
(3.408)

R ' = R 2 = R 3 = R4 = Rt ) = H

gaiangin

R ' = R 4 = R5 = H , R 2 = R 3 = M e
5 = HT
4 R=
R ' = R 2 = R3 = R
R'

= R2

3=
R

5 =H
R
3

M
E

,R4=OH

kaempferol

R = R 2= H , R - M e . R 4 = O H r h a m n o c i t r i n
1
3
R =R =R4 =H, R =Me, R 5 =

R'=R =R =H
2
3
R'=H,R =R =Me
2
3
R'=Me,R +R =CH2

(3.401)

R=H, karanjonol

(3.402)

R=Ac

( 3 . 4 0 3 ) R = C H 2C H = C H 2

(3.404) R ' = R = R = H g l e p i d o t i n
1
2
3
(3.430) R = M e fR = O H tR = 0 M e
rhynchospermin

(3.412)
(3.411)

Lilaline

(3.413)

(3.409)
(3.410)

R'=R =H,R =OH

R'=R =H,R =OMe

R'=OH,R =H
2

R'=H,R =0H

147.4

146.7

147.5

153.3

155.6

3..418

3..418

3.,419

3.,420

3.,421

3.,422

3.,423

3.,424

3. 425

3.425

3. 42 6

3.42 7

3.428

149.7

149.3

147.3

156.6

146.9

3. 425

147.1

151.2

147.1

146.9

142.0

147.3

150.1

3..415

146.9

3,.414

148.3

3..414

3..416

136..5

147.5

3,.414

3..417

140,.7 177.5

147.9

176 .5

176 .5

137.1

176 .0

175 .8

168 .1

136. 0

142.2

162,.6

164.1

164,.0

164.5

166,,0

163,.8

164.3

164.1

163 .7

C-7

95 .9

98 .6

97 .3

97.4

97.5

161..7
98,.5

98,.5

133 .1

92 .6

93 .9

91 .8

91 .8

92 .0

91 .8

94 .8

92 .2

93 .5

93 .8

93 .6

93 .6

163.,0 105 .5

C-3'

C-4'

C-5'

104.9 111,.1 158,. 1 104.9

160.9

109.2

104.0

104.2

121,. 0

157,.3

103.1 122,.1 115,.2 145,.1 147 .7 115.7 120..1

123,.7 116 .5
, 145,. 7 148 .0 116 .9 122 ..0

123,.0 116,. 0 145.7 148 .1 116.5

107,.5 157,.3 107,.1 131 .4 107.1

132..2

132,.3

130,.8

120..1

122..4 114..6 145..1 147 .1 115.7 119..3

103.7 121..9 115..2 145..0 147 .8 115.6

105.2

105.,7

105..6

115..9

121,.6

121.,6
103.4 122.,0 111.,8 145.,7 148,.8 115.5

129..4

121,,7
155..9 104.7 112.,1 159.,0 106..6 160,.0 108.8 131..6

156..0 106.8 114.,2 159.,0 106.,3 161,.2 108.3

157 ,1
,

157 ,1
, 103.3 121.,9 115.,5 145.,0 147,.6 115.0 120.,0

121.,6 115.,1 144.,7 148..3 115.9

122,,1 115.,2 145.,1 147,.8 115.7 120.,1

157,.2 117.3 125.,0 105.,7 153.,2 140.6 153.2

157,.2 114.7 126.,7 105.,6 153..3 140,.1 153.3

150,.0 115.1 123..7 115..5 145..2 145,.2 115.3

151..3 104.5

121..8

122..6 112..7 149..4 147,.9 116.0 122.,2

161,.0 108.8 122..3 110..8 148..8 148,.8 111.5

156,.8 103.5

156,.0 104.0 122..1 111..8 147..4 149,.0 115.6

156,.0 104.0 123..4 114..8 146..2 149,.4 111.7 119..8

156,.1 104.1 122..0 115..6 147,.0 149 .0 111.8 122..0

156.0

160,.6

61

49

183

183

180

121

91

91

59

91

56

189

31

182

31,182

31

91

31

97

130

123

21,14

97

180

C-6' Ref.

160 .4 106.0 123..6 110..2 148.6 148 .6 110.8 120..5

156 .2

C-2'

104. 1 109,.9 161,.0 103,.6 157 .1 107.6

93 .7 151,.4 103.5

162.,3 103 .9

151..6 130,.8 151 ,3

.

151..7 130,.7 151.,3

152,.5 131,.1 157.,0

157..2

156 .7

C-l f

104.8 123,.6 130,.8 116,.5 160 .7 116.5

C-10

95 . 0 161 .4 104.4

94 .5

127,.3 114 .7 164..3 100 .1

151,.8 130 .9

157 .3

156.9

161,.8

C-9

93 .4 157 .3

94 .0

94.9

106 .8

C-8

126,.4 114 .7 164..4 100 .0

150.0

164..2

164..4

164..8

164.9

164.9

97 .4 164..9

96.0

95 .5

98 .3

99 .6

99 .5

98 .1

98.7

99 .5

99 .3

C-6

120,.9 114.1

159,.0

161,.2

160.4

160 .4

160 .3

160 .4

158 .1

158.6

160 .8

15 7.5

161 .0

160 .8

161 .4

177 .8 162..6

179,.6

135.,4 176.0

135.,4 175 .9

132.,0 178 .0

135.,5 176 .1

13 3.
,2 167 .9

137.,9 172 .6

137.,2 173 .0

133.7

136..1 176 .3

136.2

136..4 176 .0

136.2

175 .9

171 .1

137..4 171 .6

135,.8 175 .9

136 ,7
, 176 .7

136.0

155 .9

C-5

176 .7 161 .3

3,.413

136.5

136,.5

149.6

149.2

177 .5

3,.412

137.1

148.5

C-4

C-3

3,.411

C-2

3,.412

Str.No. Solv.

154

155

(3.414)
(3.415)
(3.416)
(3.417)
(3.418)
(3.419)
(3.420)
(3.421)

2
3
.422) R ' = R = R = H , R = 0 H
2
3
R ' = R = R = R =R = q u e r c e t i n
(2
2
3
.425) R ' = O H , R = O M e , R = R =H
R ' = H , R = R = R = R =Me
(c
,
3
2
R =R =R^=R^=H,R =Me azaleatin
2
3
R'=R =R^=R =H,R =Merhamnetin
{I
2
4
3
R ' = R = R = H , R = R ^ = M e ombuine
1
2
3
R =R =R =rLR =RT=Me rhamnazin
2
3
R ' = R = R = R = H . R =Me
,
2
3
3
R =Ac,R =R =R4=R5=Me
R 0

(3.423) R ' = R = H , R = R = R ^ = M >

2
3
( 3 . 4 2 4 ) R ' = A c , R = H a . R = R =R =Me
3
4
2
(3.431) R ' = R = R = R = H . R = O H
3
2
(3.432) R ' = R = R = H , R = 0 H , R =Me
mearnsetin
OH

(3.427) k u s h e n o l

(3.428) k u s h e n o l G

( 3 . 4 2 9 ) R ' = R 2= H , R = O 3H g o s s y p e t i n
(3.433) R ' = R 2 = O M e , R 3= M e
(3.434) R ' = R = O M e , R = H

3. 435

3. 436

3. 437

3. 438

3. 439

3. 440

C-4

147. 5

147. 8

140. 6

140. 0

143.2

143. 7

3.419 55.8;

3.403 72. 4, 117.6, 133.6;

29.5;

C(Me) 2C=CH

131.6, 25.8, 17.8;

3.430 56.1;

3.398 56.4;

3.432 59.6;

C H C H 2C H 2C O N H :
3. 427 28. 1, 47.9, 148.9, 19.2, 111 .5, 32. 1, 124. 1 ,

3. 440 28. 0, 122.9, 130. 1 , 25. 4, 17.7;

CH 2CH(C(Me )=CH 2 )CH 2CH=C (Me ) 2 :

Me:
3. 402 104.2, 147.3;
CH.CH=C (Me ) n : 3. 439 29 .2 ,

3.401 104.1, 146.3;

3.340 118.9, 130. 7, 76.6, 28. 0;

CH=CH(0):

3.395 168.1, 20.2, 21.2; 3.402 167.7, 20.1;

3.437 56.0,

3.433 55.5, 60.2,

3.408 55.3, 55.9;

3.439 40.5, 28.0, 27.4, 148.5, 113.1;

3.440 40.5, 27.6, 27.8, 148.5, 112.7.

CH 2CH(C(Me )=CH 2 JC^CH^C (OH) (Me),; 3.428 27.8, 48.2 , 148.7, 18.6, 111.5 , 28.3, 42.5, 70.8, 29 .8,

3.411 48. 1, 35.9, 38.5, 183.9;

121..5 119..4 140 .9 142 .3 115..3 128..7

3.418

188
188

113..8 130..8

104.,7 121.. 4 126..4 141 .5

3.407 56.0;

142

140.,6 110..2

110..2 108..4 152..9 100 .5 151.9

144.0

142

112.,7

104.J

142

143..2 110.,0
140.2

113..8 110..3 151..8

98 .3 152.6

142

143..7 110.,0

113..3 109..8 152..3 102 .1 153.2

187

115.,7 120.,0

98 .2 152.2

105..1 110..8 151..8

115..6 121..6

102.,3 122..1 114.,9 145 .1 147.8

186
187

107..1

125.,7

136.1

102..3 122..1 111..2 147 .4 148.8

121..2 107..5 146.0

102,.9 119..8 107..1 12 5.7 150.3

103.3

146..0 107., 7 104,186

3.436 56.1, 56.3, 56.7, 57.1, 61.6, 62.2;

OCOMe:

3 . 405 101.6;

CH=CHC(Me),:

OCl^O:

122.9, 132. 1, 25. 4, 17.7, 26.2, 121. 1, 134.2, 25.6, 17.9;

OCH_CH=CH ?:

3.411 17.5;

C-6* Ref.

184

C-5'
179

C-4'

110..8 120..9

C-3'
115.,3 120,.2

C-2'

103,.5 124..5 114..7 145 .8 150.9

C-l'

102..7 124..7 115..5 145 .0 147.7

C-10

3.426 55.7, 60.0;

3.438 56,3, 56.4, 56.6, 61.5, 62.5;

3.405 20. 4;

56.3, 61.4, 62.1;

3.398 7.3;

3.425 59.9;

3.397 56.1, 56.9;

155.1

109.7

3.435 56.0, 56.2, 56.3, 56.7, 60.9;

3.420 56.2;

3.394 56.1;

161.1

100.4

135.,7 175 .0 158.8

174.9

155.1

161.1

100.5

158.9

135.,6

109.6

154.3

154.0

140.0

139.9
96.2

138.,1 171.5

153.2

152.6
158.0

158.0

159.0

139.8

90.8

127.7

159.4

144.3
144.4

127.6

156.1

156.4

154.0

132.4

147.2

147.2

93.1

93.5

154.4

138.,4 172.1

138.,2 171.5

3.434 60.2. 61.2;

55.9, 56.0;

61.0;

130.9
130.9

164.1

164.2

144.8
156.0

122.3

152.1
15 1.8 108.2

C-9

C-8

C-7

96.2

151.8

146.9

146.6

98.0

98.5

94.6

98.1

C-6

96.2

175.8

176.2

160.4

161.0

159.2

152.6

C-5

158.0

136..6

135,.5

135..5

176.2

150 .4

150 .5

176.0

136..4 175.8

147. 1 136.1

145. 8

175.9

135..4 176.1

C-3

136.9

148. 9

146.6

C-2

Other signals: OMe: 3.392 56.0;

3. 432

3. 431

3. 434

C+D

3. 430

3. 433

3. 429

Str.No. Solv.

156

157

(3.435) R=H
(3.436)

R=Me

(3.437)

R=H, R = M e

(3.438)

R =Me,

R =H

(3.439)

broussoflavonol

(3.440)

broussoflavonol

C^q

terpene

substituent

are

shown

by

C-8

isoprenyl

flavono]

substituent

such

of

C-8

the

unusual

which

(3.411)

position
with

3.406

meta

effect

furan

ring

exhibit

of t h e

for

C-7

and

Thus

C-8

(3.390)
alkyl
Both

in

al.

13.4

ppm

of

It

These

can

also

be

nic

carbons

ring C. The
ppm

are

The

may

at

be

and

of

nullify each

a l s o not

men-

The

93.0

ppm

reason

for

mentioned

[38].

of

substituent

at

flavonol

C-8

position

C-8

resonance

and

field
3.411

negligible

with

can

be

considered

considered
as

as

an

the

C-3)

and

shift

ranges,

for

position
to

the

as

and
in

almost

and

of

resonances
ppm

unsubstituted

equal

ipso
of

the

105.01.0

ring A
1170.4

oxysubstitution

the

substituent
as

are

[172].

flavonol

effect
the

carbonyl

category

appear

C-3

resonance

at

of
of

of

furan

ether.

the
ring.

3-methoxy-

flavones

Thus

135.7-141.4

of t h e

as

but

flavonoids.

(C-4) constitute

150.6-160.5,

appearance

designated

subcategory

flavonol-3-0-methyl

chemical

3.5)

substituted

157.60.3

independent

( C - 2 and

characteristic

ring

resonances

oxymethine

other.

3-methoxy

compounds

methine
for

3-METHOXYFLAVONES

resonances

two

the

oxyolefi-

heterocyclic:

and

C - 2 , C - 3 and

167.1-180.0

C-4

resonances

[56,5 7,95,110,166,168,172,173,177,185-199].
at

around

around
33

8.0

ppm

and

11.0

downfield

ppm

we

These

Thus

upfield

shifted

shifted

position

in

compounds r e l a t i v e to f l a v o n e s (see s e c t i o n 3 . 4 ) . H o w e v e r , a c o m p a r i t h e 13 C c h e m i c a l s h i f t s o f u n s u b s t i t u t e d
3-methoxyflavone (3.441)
with

unsubstituted
C-4',

above

position,

characterization

at

due

effect

C-4

son

field

3.403 ,

furan

same

perhaps

ortho

C-2,

these

the

5,7-dihydroxylated

substituent.

145.31.1

appear

the

(Table

whereas

is

on

to

methine.

respectively
and

high

the

3.401
limits

compounds

effects

these

to

C-8

narrow

almost

Flavones

treated

exception

prenyl

oc - e f f e c t

3.6

flavones.

having

resonance.

absorbs

of t h e s e

behaviours

(3.440)

r e s o n a n c e at s i g n i f i c a n t l y low
13
c o m p a r i s o n of t h e
C c h e m i c a l s h i f t of

these

[168].

reported

Thus

within

substitution

an

3-methyl-2-oxo-pyrrolidinyl

nonoxygenated
C-8

shielding

broussoflavonol

C-8 resonance

furanoflavonols,

occur

8-C-alkyl substituted

bears

appearance

on C - 6

and

significantly

C-8

et_

ppm.

In

ppm

the

Similar

represents
for

at

that

having

to

106.8

(3.404)

absorbs

fact

behaviour

lead

(3.439)

behaviour

Masterova
alkaloid

position.

[188].

shielding
as

inspite

C-8

broussoflavonol

Glepidotin
13 C

tioned

at

C-5'

flavone
and

C-6',

(3.171)
C-7,

reveals

C - 8 and

that

C-10 are

ring

resonances

negligible affected

( C - l 1,
({ <

C-31
ppm),

159

whereas
-8.5;
+1.9

remaining

C - 3 , +33.1;
ppm)

the

nances

shift,

The

cyclic

aromatic
attached

at

no o r t h o

to

at

di-ortho

signals

of t h e

hence

its

The

be

of a l k y l

methine

i.e.

on

the

at

so

carbonyl

in

of

Thus

ppm

absorb

at

are

chemical

or

C - 6 i n c a s e of 8 - C - a l k y l a t e d c o m p o u n d s

position

acetylation
other

at

and

of
H-5

ca.

98

therefore

can

readily

unsubstituted

and

in

ppm.

positions

of

carbonyl
hydroxyl

with

compounds

shift

insensitive

with

8-C-alkylated 3-methoxyflavone
the

at
or

5-hydroxylated

174.02.0

distinct

the

groups

one

of t h e

shifted

Methylation
at

with

downfield

3-mehoxyflavones

resonance

3-methoxyl

bearing

in

upfield

hetero-

methoxyl

interactions

5 ppm

appearance

overlap

C-3 resonances

5,7-dihydroxylated

in 6- or
basis

not

carbons

178.5 1 . 5

that

the

chemical shifts

hydroxylation.
C-4,

is

considerably

bonding

about

C-8 resonances

substitution

determined

hydrogen

C-5
on

respectively

but

reso-

C-10 [168].

of a r o m a t i c

to

of

(3.390)

C-9

of q u a s i - a r o m a t i c

does

occur

C-2/C-6'

flavonol

substituted.

attached

C - 2 and

absorbs

identical

C - 6 and

ppm

compounds

(C-2,

shifts

C - 2 , C - 4 and

C - 3 and

because

di-ortho

rings

relatively

effect

OMe-5 h a v e nearly

by

C-4

lacking

site

aromatic

C-9, -9.3;

NMR c h e m i c a l

the

generally

those

chemical shifts

position

is

carbons

of

of t h e

The resonances

ppm).

(C-4) is influenced

93

as

(55.51.0

in both

of

these
It

and

substituted

from

eliminates

ca.

of

ppm

ppm

ppm.

[187],

3-methoxyflavones

and

feature

position

whereas

or

2.2

the

alteration

with unsubstituted

4.6

and

notable

C-6, - 3 . 2 ;

of

(3.441)

and

59.50.5

3-methoxyflavones
OH-5

1.7

groups

substitution

C-5

at

substituents

resonance

5.9

C-3 methoxyl acts

ppm)

The
to t h e

shift

distinct

methoxyl

(61.51.5

8.5,

show

C-5, -3.7;

comparison

diagnostic
group

ring C and

resonates

-11.3;

Similar

downfield

3-methoxyl

resonances

3-methoxyflavone

upfield

and

carbon

C-4,

[3.168].

unsubstituted

suggests

of

other

aryl

C - 8 in 6 - C - a l k y l a t e d

compounds.
In

the

NMR s p e c t r u m

5,7-dihydroxylated-3-methoxyflavone
at

99.1

C-8
of

as
both

ppm
the
C-6

appearance
in
are

c3

corresponding
site
and

of

haplopappin,

C - 6 and

there

signal

positions

in

broussoflavonol

at

112.0

the

of

C-6

and

identical

C-8

and
is

[194].

107.1

As

an

C-alkylated
aryl

ppm thus
The

(3.506)
ppm.

maintained

substituents.

novel

exists

at 1 1 1 . 3

substitution

resonances

shifts
with

to

-methylbenzyl

C-8

these

chemical

substituted

of

of

(3.458),

when

revealing

C-prenylation
results

Hence,

mentioned

methine

C-6

to

the

difference
and

C-8

already

that

152.0

155.2

153.9

151.8

157.3

155.1

155.3

154.1

155.2

155.3

MC

3.444

3.445

3.446

3.447

3.448

3.449

3.450

3.450

3.451

3.452

3.453

3.454

3.455

3.456

155.6

3.459

155.4

155.3

C+D

3.45 7

3.458

156.2

153.0

152.9

153.8

155.4

155.6

3.443

154.7

3.441

C-2

3.442

Str. No. Solv.

137.7

135.7

137.5

137.9

137.3

137.6

138.7

137.5

140.7

138.1

137.8

139.4

140.0

140.0

141.0

138.9

141.4

141.1

141.9

140.7

C-3

C--5

C--6

C--7

133. 8

98.8

98.5

97.5

177.9

178.9

178. 0

178. 2

98. 5

161..2
164..1

93. 6

156 .3

162..2 111. 3 161 .5

148 .5

158 .2

144 .8

94. 1 151 .6

98.,8 156.,9 127. 5

99. 1

157 .7

156 .6

161 .2

158 .3

152 .6

146 .9

149 .1

161 .4

94. 3 156 .8

98. 6

94. 0

93. 8

95. 7

92. 8

153,,1 124. 8

157,,8

157.8

164.3

163..1

164..4

164.4

167.,1

140.,4

165,.5 120. 9

98.,8 147.,8 128. 6

98. 4

155,,9

155..9

155,.3

178.,1 152..7

178.,2 152,,3 131. 3

179.,8 153..6 131. 7

176.,0

173.,0 150..5 107.9

178. 1 161..5

177.,8 156..4

179.,6 163,.1 100. 7

172,,7

172.,9 126,.2 108. 0

9-3.9

157..3 116.6

98 ,8
, 164.,5

155 .7

155 .6

92. 1 158 .4

132..9 117. 8

95.,5 163,.5

173,,4 120..8 109.6

178..2 156..7

173.,6 160..5

C--9

118. 4 147.0

C-8

126..8 124,,5 133..1 118. 0

174.,4 125..4 124.2

174.8

167.,1 122,.0 122.,0 134.0

C--4

Carbon-13 NMR chemical shifts of 3-methoxyflavones3

TABLE 3.5

C--1'

C-3'

C--4'1
C--5'

130,.1 114.3

161. 3 113..9 129 .8

161. 5 114.3 130,.1

187
189

161.,4 114.3 129 .7

104..2 120..8 115 .4 145.2

105..4 122..9 130 .3 113.9

148. 6 115..7 120 .6

159. 8 113..9 130 .3

187

194

187

193
160. 1 115..5 130 .2

192

191

56

104.185

189

110

190

161. 3 114..2 129 .9

104..0 120..7 129 .9 115.7 160.2 115..7 129 .9

104.,7 122..3 129 .7 114.2

103..9 120..8 130 .2 115.5

104..5 122..2 129 .9 114.2

106,.2 122..6 131 .1 116.7 160. 8 116..7 131 .1

130..8

110..5 122..9 129 .8 113.9

104..5 124.5

129,.9

162. 1 117.,5 131 .9

104..1 122..1 129 .9 114.4 161. 4 114.2

105.,7 122..4 131 .9 117.5

119,.6 129..8 127,.4 127.8 129. 6 127.,8 127,.4

167,173

173

117.,8 130..3 127.7 128.3 130. 3 128.,3 127,.7

104,185

87,170

142

119..0 130..3 127,.8 128.3 130. 3 128.,3 127,.8

127,.7 128.0 129. 0 128.,0 128,.7

142

104.6 130..2 128 .2 128.8 131. 1 128.,8 128,.2

109..1 130.5

124,.2 117..8 157,.0 111.1 131. 6 120.,1 130,.1

174

C--6' Ref.

128 .2 128.6 130. 8 128.,6 128,.2

C--2'

124..5 118..0 156,.4 113.1 131. 8 120.6 130,.9

123.,5 130.5

C--10

160

161

R 0

OMe
2

(3.441) R=H
(3.442) R=OH
(3.443) R=OMe

(3.444) R ' = R = M e , R = H
2
3
(3.445) R ' = R = R = H
2
3
(3.449) R ' = R = H , R = 0 H
isokaemferide
f
2
3
(3.450) R = R = H , R = O M e ermanin
2
3
(3.451) R ' = A c , R = M e , R = O M e

(3.446) R ' = R = H k a r a n j i n m e t h y l
2
(3.468) R ' + R = 0 C H 20 p o n g a p i n

ether

(3.447)

dihydrokaranjin

methyl

ether

R 0
2

R 0
1

OR

2
3
4
( 3 . 4 4 8 ) R 1' = M 3e , R + R2 = C H 2 R = H
( 3 . 4 5 3 ) R 1 = R 3 = H . R 2 = M e f R =OH
( 3 . 4 5 4 ) R = R = H , R = M e , R4=OMe
OMe
2

R 0

OH
2

( 3 . 4 5 5 ) R ' = R = R = R =H
2
3
3.456) R ' = H , R =R =R4=Me f l i n d u l a t i n
2
3
( 3 . 4 5 7 ) R ' = R = R 4 = H , R = Me

(3.458)

haplopappin

3.,468

3. 469

3. 470

3. 471

139.2

C-3

137.9

138.6

140.3

138.3

151. 3 139.5

3. 478

137.6

154. 9

151. 4 138.0

3. 477

155.,9 138.9

155.,3 138.0

155.,9 137.7

155.,5 137.3

153.,7 141.7

155..3 137.6

152..9 140.9

155..3 138.0

153..0 141.2

153..8 140.6

153..7 140.5

155..4 137.7

155,.8 137.9

155,.4 137.7

154,.9 137.9

155,.1

154 .9

151 .2

154.5

151 .8 140.6

157 .8

C--2

3. 477

3. 477

3. 477

3.,467

3. 476

3.,467

3.,466

3. 475

3,,465

3.,464

3. 474

3..463

3..462

3..461

3. 473

3,.460

3. 472

3,.459

Str.No. Sol .

160.9

161.3

161.2

161.2

161.0

160.1

161.5

158.2

163.2

C-5

151.2

172.,0 152.3

180.,0 151.9

177.,9 151.2

178..9 152.3

178..1 151.6

178..0 155.4

178..3 147.9

173..0 150.1

177..7 161.5

172,.9 150.7

177,.8 160.8

172,.4 150.5

173,.2

173,.4 120.9

177,.8 160.8

178 .

177 .9

177 .8

177 .8

178.0

171 .9

178.0

172 .1

179 .4

C--4

150.7

156.4

164.0

163.2

164.9

163.4

163.2

157.4

164.3

165.1

164.1

164.1

164.8

165.2

163.5

164.3

163.8

164.7

C-7

139..9

131..5

131..3
152.9

158.0

158.2

132.,4 158.8

131..7 158.6

98..8 156.8

131,.3

113,.2

98,.5

108,.0

97,.5

108,.1

108 .0

109 .7

97 .4

97 .8

98 .5

98 .6

98 .7

97 .8

95 .7

98 .8

96 .2

99 .3

C--6

160 .1

156.5

160 .0

162 .3

C--9
C--1'
C -2'
C--3'

C--5'

104 .6 123,.9 107.9

108 .3 122 .7

122..1 111 .2 148.2

151 .0 114 .4 121 .1

112.1
147.5

150 .0 115 .7 122 . 3

122.,1 112 .1 147. 3 149 .6 115..5 120,.8

105..6 122. 1 111 .6 148. 5 151,.4 111..6 121,.9

104..1 121.,0 115 .3 145. 3 148,.8 115..9 120,.6

103..5 120.,7 129 .9 115. 7 160,.2 115..7 129,.9

113,.2 128.,8 112 .4 151. 0 143,.5 122..9 121,.2

104.1

111,.1 122.,7 123 .0 139.5 152 .7 112,.0 127.4

105,.0 120..2 115 .0 146.2 150 .1 111,.7 121 .1

111 .0 129..2 112 .6 151. 1 141 .6 122,.9 121 .1

150 .5 111,.4 121 .9

107 .9 147. 6 149 .3 108,.2 123 .2

111 .0 123..1 111 .0 148.8

119,.1 124.1

105 .0 122..1 112 .1 147. 3 149 .7 115,.5 120 .7

105,.2 120.7

104 .2 122..2 112 .0 147.4 149 .7 115 .6 120 .9

104.2

104 .0 122,.3 114 .9 146.,3 150 .2 111 .9 120 .3

105 .4 123,.5 107 .9 147.,7 149 .5 108 .4 123 .5

148.4

147.,7 149 .4 108 .3 123 .3

107 .7 123.,9 108 .3 147.4

96. 9

89. 8

157,.3

155,.0

91.,0 151,.2

150 .8 110..3 121,.5

111..1 122.,5 111 .9 148. 4 150 .7 112,.1 121,.4

105..7 122. 1 110 .7 148.0

105..3 121.,6 111 .5 148.2 151,.2 111..5 121 .6

189

87

103

132

132

187

187

56

56

56

56

56

56

173

56

182

86

189

193

104,189

189

189

189

192

C--6' Ref.

149 .0 116 .2 123 .0

C -4'

109 .0 123,.1 111 .3 149..9 151 .2 112 .3 121 .6

105 .8 122,.1 115 .7 145.2

C--10

90.,4 152,.8 106..6 123.,0 110 .9 148. 9 151,.5 111..4 122,.0

91.,3 151,.5

127.,6 148,.5

127.,7 144,.2

108.,8 158,.3

93.,7 156,.2

98.,5 157.5

91..9 156,.0

98..6 157 .7

98,.6 157 .7

116..7 149 .1

92..0 155 .9

92..4 156 .3

93,.8 156 .3

93,.8 156 .2

93,.7 156 .4

92,.4 156.3

92,.9

93,.9

93,.4

94,.3

C--8

162

163

OR
2

HO

R 0

(3.459)
(3.460)
(3.461)
(3.462)
(3.463)
(3.464)
(3.465)
(3.466)
(3.467)
(3.469)
(3.470)
(3.471)
(3.472)
(3.473)
(3.474)

Me
2
3
4
=R =H,R +R =CH2
2
3
4
isokanugin
=R =Me,R +R =CH
2
3
4
=H,R =Me,R +R =CH
2
3
= R = R = H , R =Me
2
3
4
= R = H . R = R = Me
2
4
3
=R =R =H,R =Me
4
2
3
=R =H, R =R =Me, pachypodol
2
3
4
=Ac,R =R =Me,R =H
4
2
3
=R =Ac,R =R =Me
3
2
4
(3,
^.R =H,R =R =Me
3
2
4
(3.
=R =Ac,R =R =Me
2
4
3
(3.
=R =R =H,R =Me
2
4
3
(3.
=R =R =Ac,R =Me
(3.
(3.
(3,
(3.
2
OR
OR

(3.475)
(3.476)

OH

2
R'=OMe,R =H
2
R'=H,R =OH
OR

R 0

MeO-

477)
478)
479)
480)
483)
484)
486)
487)

R'
R*

R
R'
R'
R'
R'
R'

= H fR = M e tR + R = C H 2 Melisimplin
2
3
4
--R = M e , R + R = C H 2 m e l i s i m p l e x i n
2
3
4
=R =R =R =H axillarin
2
3
=R =R =H,R=Me
centaureidin
2
4
3
R =R =H,R =Me
3
2
4
= R = H , R = R = Me

MeO

(3.481)
(3.482)
(3.485)

R'=H,R +R =CH2
2
3
R'=Me,R +R =CH2
meliternatin
2
3
R'=R =R =H

R'=OH,R =H
2
R'=H,R =0Me meliternin
2
R'=R =0Me,
melibentin

MeO

R Q

OH
(3.490)

(3.488)
(3.489)
(3.50.7)

chlorflavonin

( 3 . 4 9 1 ) R ' = R 2 = R 3 = R =D 5R = H
( 3 . 4 9 2 ) R ' = R 2 =R 3 = R4 _B = R = Me
( 3 . 4 9 3 ) R ' = R 2 =R3= R = ,3H R 4 = Me
( 3 . 4 9 4 ) R ' = R 2 = R 5 = H , R = R =Me
1
5
2
3
4
(3.495) R = R = H , R = R = R = M e

155 .6

151 .5

155 .1

153 .3

3,.481

3,.482

3,.483

3,.483

3,.484

155 .1

151 .8

151 .2

155 .6

155,.5

3..487

3..488

3..489

3..490

3..491

3..492

3.,493

160,.5

154,.9

3.,496

3.,496

3.,497

172,.9

152,.2 141.7

156..2

97,.6

95,.0

150..0 108,.3

160..9
163,.4

165,.1

162,.9

164,.4

99,.4 164,.8

163..1
98.7

99,.8 165,.7

162..9

C-2'

C-3'

C-4'

C-5'

C-6' Ref.

104..5 120. 8 115,.7 145.,2 148..6 115.,4 120..6 183

104..4 120. 9 115 .7 147.,3 148..8 115..4 120..5 193

113..0 124. 0 107 .8 147,.7 149..1 108..3 122..9 189

107,.9 123. 8 107 .9 147.. 7 149..5 108..4 123..2 189

112,.1 123.,9 107 .8 148,.5 149..0 108..4 123..0 189

115,.4 145.,1 148..7 115..6 120.,5 196

107,.8 147,,5 149.,0 108.,3 122.,8 189

121 ,7
. 132..1 120 ,. 1 163 .9 197

121.2 115 .7 145.,2 148..7 115..7 120.,9 187

158.3

106.,4 123. 4 129,.0 144.,4 147..3 113.,2 123.,8 198

158.,6 106..1 122. 8 129,.4 144.,6 148..1 113.,1 123.,9 198

115.,8 120., 1 167

124.7

104,.9 152.,0 138..2 152,,0 104.9

95
98.,5

157.,6 111.,2 128. 6 109,.8 152.,1 133..7 143.,3 115.,3 56

92.,2 156.,2 104.,5 119. 6 105,.1 148., 1 138..1 145..6 109.,8 56

92.,9 157.,4 107.9

94.,1 156.,5 104.,4 125.2 106,.0 152.,8 140..0 152.,8 106.,0 185

94.6

94.9

150.6

104..0 120. 9 111,.6 147.,4 149..7 115..7 122.,0 187

103..9 121. 1 112 .3 147..4 149..7 115.,6 122.,4 187

108..0 122. 6 110,.5 148,,3 150..6 111.,7 122.,2 167

104.0

105..2 119. 9 151 .0

107..5 124. 2 108,.6 147.,7 149 ..1 108.,6 122 ,

. 7 189

122.,3 124.4

105..3 122. 0 111 .4 146.,0 149..9 111.,7 120.,1 103

120. 8 112 .0 147.,4 149..7 115.,6 122.,1 187

107..0 120.5
104.3

128.,2 158.,0 104..4 122. 2 111,.1 147.5

127.,4 148.,5

147,.5

98,.7 156,.8

156..2 195,.6

155..1

146,.1

125..0 144.9

128.,4 148..8

129.,9

96.,4 150..0

90..8 158..2

129.,5

159..5

3.,500

155..9

124.,7 143..9

153

158 .2

150 .0

89..3
94.. 1 151..5

153,.3

171,.6

177,.9

140.1

155,.8 138.0

150,.6

C+D

155 .1
144 .4

C-l'

94..0 151..7 104..3 122. 4 114,.9 146.,4 150..2 111.,9 120..3 193

149,.9

93 .1

98,.4

95 .8

93 .8

137.3

151..6

98,.5

161..3

140 .4

155,.1

157.4

93..8 157,.2

93..9

C-10

158,.7 105,.7 123.,5 107 .9 147..9 149..5 108..4 123..5 189

C-9

93,.4 153..1

90,.9

97,.0

98,.8

C-8

152,.8

155,.6

152,.8

156,.6

155,.7

153.5

155 .6
158 .0

131 .2. 157 .8

129 .0

131 .3

151,.4 131 .2

152,.2

151,.5

152,.2

131 .1

157 .9

152,.3

152 .7

152 .8

152 .2

154 .9

C-7

152,,4 131 .3

129 .3

138 .5

131 .8

C-6

152,.7 135 .5

152,.0

151,.8

151 .6

C-5

178,.1

179,.6

3.,498

138.6

140.3

180,.0

3.,499

161,.6

140.4

178 .0

178.0

137.4

3.,495

155,.6

3.,494

155,.8 137.6

172 .2

178 .2

178 .6

172 .2

172 .1

177 .9

178.0

178 .3

178 .1

178 .1

178 .1

172 .2

178 .4

171 .9

178 .2

C-4

178 .1

139.9

137.5

139.4

140.1

140.1

137.6

137.3

137.5

137.6

137.3

137.3

140.3

138.4

139.9

138.8

C-3

137.5

155,.2

151 .3

155 .3

3,.485

3..486

151 .7

154.5

151 .2

151 .6

3 .479

C-2

3,.480

Str.No. Solv.

164

165

OME

OH
(3.496)

podoverine A

(3.506)

R'=R =H,R =Me

2
3
R'=R =R =Me
3
2
Me
R f' = R3 = H , R =
22
3
R '= R
R ==AAnc.,RR ==M
Mfei

(3.505)

broussoflavonol A

(3.509)
( 3 . 5 1 31 )

broussoflavonol

. O R

(3.510)
(3.512)
(3.513)
(3.514)

R'=H,R =R =Me
2
3
R' =OMe,R =Me.R =H
2
3
R'=OMe,R =H,R =Me
2
3
R'=OMe,R =R =Me

(3.497)
(3.498)
(3.499)
f( 3 . 5 0 001)

R ' = R 3= M e , R2 = H b r i c k e l l i n
R'=R =H,R =OMe

138,.1 178. 0

C-4'

C-5'

107,.7 122 .8 111 .2 148,.9 149 .4 115.,0 123,.1

103,.4 120 .9 115,.2 145..3 148 .8 115. 8 120,.5
105..6 123 .2 116,.3 146.1

149,.3 116.3

159.,0

3.471 55.5, 55.8, 59.5;

3.445 59.6;

3.473

3.467 55.7, 59.4;

3.449 61 .5;

55.7, 59.5;

3.468 59.3;

188

3.464 59.7;
3.474 56.0, 60.2;

3.475 59.6,

3.470

3.465

3.457 59.6, 61.0;

3.450 55.3, 59.7;

3.469 56.0, 56.1, 60.0;

3.463 56.0, 59.7;

3.456 55.3, 56.5, 60.9;

3 .447 59 . 5 ;
3.462 56.0, 59.1;

3.472 55.9, 59.8;

3.467 55.7, 56.0;

3.466 55.7, 59.6;

55.6, 59.7;

3.461 59.7;

3.446 59.5;

113.,0 157.,9 106.,1 120,.1 121..4 143.,6 145..8 112. 9 129..3

3.454 59.7, 59.9;

3.460 55.9, 56.2;

187

187

164.,3 113.,6 159.,1 106.,6 122..0 125..9 149.,0 150..6 111. 6 131..4 188

3.443 55.4, 60.3;

3.453 60.1;

187

187

150.,8 127.,7 144.,5 103..4 119,.7 105..8 147.,8 139,.0 147. 8 105,.8 187

102..6 107,.1 152..9 104.,1 150,.3 140. 5 114..5

125,.2 105..6 152.,7 139,.9 152. 7 105..6

90.,7 155..9 106..3 108,.6 152,.7 103..0 153,.9 143. 0 111..3 200

157..3 127.,5 148..6 104.1

95.,9 163. 5

3.459 60.1;

3.442 60.3;

160.2

96., 3

189

199

199

199

152..4 132..4 144..4 106..8 122,.1 110,.9 148..5 151,.4 111. 7 122..0 187

114..4 123,.9 107,.5 147..5 149,.2 108. 6 122..9

122..0

122,.0

187

187

198

187

187

C-6' Ref.

106,.7 120 .6 111 .7 147,.5 150 .1 115.,8 122,.3

157..7 106..0 123,.1 116,.5 146..2 149,.4 116.5

156..9

146..1 137..4 147.3

160..0 107.,0

157..4 108..1

C-3'

155..8 104,.4 120 .5 115,.8 145..4 148 .9 115. 6 121,.1

150..7 127..7 144,.5

155..9 106..9

C-2'

140,.7 103,.3 121 .0 115,.5 145..5 148 .5 115. 5 120,.7

145,.6

C-l'

103,.4 120 .9 111 .6 147,.4 149 .8 115.,8 122,.1

C-10

147.,9 131.,4 151.,0 127.,7 144.,6 103.,6 125,.2 105..6 152.,7 139..9 152. 7 105..6

3.459 59.7;

55.9, 56.0, 60.2;

123,.1

132,.4 144,.3

146,.7 125,.2

146,.8

152,.3

144,.5

C-9

147.,9 131..4 150.,7 127.,8 144.,6 103..6 125..1 109..7 150.,9 138,.9 153. 0 103..9

147.,9 131..3

3.451 55.3, 55.9, 59.9;

Other signals: OMe:

154. 1 138.,4 178. 5

C-8

150,.8 127,.7

C-7

147.,9 131..7 150.,8 128.,0 145.,3

98..9

151..2 132..6

148..1 135..5

150..8 143..2

156..8 112,.0

155,.1 106,.2

138..9 179. 4 161.,0

154.,4 138..3 178. 4

154.,7 138..2 178. 5

3.516

3.513

156.6

154..9 137..6 178. 3

154. 8

131,.3

171,.1

133 .1

133 .6

131 .3

C-6

153,.4 104,.9

147,.9

144,.5

155.,9 138,.5 178. 1 154..3

177. 4

155.,5 138,.0 178.6

152.,2 140,.0 172.2

153..1 139,.0 179. 8

154..3 139,.2 179. 9

3.511

3.512

178.3

152..7 137 .7 178. 4

143.,0 136.6

148,.1

179.,5 153,.1

155..4 137 . 3 178. 3

155,.4 137 .0

138.9

137 .7 178.5

3.510

155,.9

156,.1

C-5

178.,3 147,.9

C-4

3.515

3.509

C-3

155,.2 137.4

C-2

3.514

3.506

3.507

3.505

3.508

3.505

3.503

3.504

3.502

3.502

3.501

Str.No. Solv.

166

3.479 101.2;
3.507 101.8.

3.468 101.6;

3.489 101.7;

3.463 101.8;

3.488 101.7;

3.462 101.7;

3.485 102.7;

3.461 101.9;

3.482 101.1, 102.5;

O C H 20 :

3.480 101.7;

3.516 40.9, 27.7, 27.8, 149.4, 107.

3.516 119.0, 130.4, 75.6, 29.4x2.

3.505 115.0, 121.1, 77.7, 27.7x2;

3.515 40.5, 27.4, 28.0, 148.5, 113.1;

C(Me) 2CH=CH 2:

3.516 28.3, 122.8, 130.9, 25.3, 17.8.

CH=CH-C(Me) 2:

17.9;

3.505 21.1, 122.0, 131.0, 25.5, 17.8;

3.506 22.6, 123.5,

3.481 101.7, 102.3;

3.515 29.2, 122.9, 132.1, 25.4, 17.7, 26.2, 121.1, 134.2, 25.6,

3.496 26.8, 122.7, 132.0, 25.7, 17.9;

132.7, 25.8, 18.8, 22.2, 123.1, 132.4, 25.8, 18.2;

CH 2CH=C(Me) 2:

3.468 104.0, 146.7.

3.515
3.470 168.4,
3.500 167.3, 168.2,

3.469 169.4, 21.1;

3.474 167.9, 168.5, 169.2, 20.6, 21.0;

3 .458 31.8, 18.1 138.2, 127.9x2, 115.0x2, 154.4.

3.447 25.7, 72.9.

CH 2CH 2(0):

CH(CHJC^H C:

3.446 114.0, 146.7;

169.4, 20.2, 20.6, 21.0.

3.472 168.6, 169.4, 20.6, 21.1;

3.451 169.4, 21.1;

3.514 55.9, 59.9, 60.2, 61.1;

3.511 56.5,

3.507 59.4, 61.3, 61.4, 61.8;

3.510 55.9, 59.9, 60.2, 60.8;

3.506 60.1;

3.513 55.7, 59.9, 60.1, 61.2;

OCOCH3 :

3.512 56.0, 59.6, 60.1, 61.1;

3.516 55.4, 56.2, 60.3;

55.7, 60.6;

CH=CH(0):

3.505 60.2;

3.502 55.5, 59.6, 60.5, 61.4, 61.8;

3.499

3.493 55.8,

3.487 55.1,

3.482 59.4,

3.498 55.2, 55.4, 59.6;

3.492 55.6, 56.1, 59.2, 60.8;

3.486 55.7, 59.6, 59.9;

3.496 60.5;

3.501 55.5, 59.6, 60.1, 61.1;

3.505 59.6;

59.9, 60.8;

169.4, 20.6, 21.1;

3.491 59.7;
3.496 60.9;

3.509 56.0, 56.4, 56.8, 60.9, 62.1;

3.504 59.6, 60.1, 61.2;

3.500 56.0, 56.2, 60.2;

3.508 55.7, 59.7, 60.6, 61.4, 61.7;

3.503 59.5, 60.0;

56.4, 59.2;

3.495 55.5, 56.4, 60.9;

3.488 56.4, 59.2, 61.2; 3.489

3.494 55.5, 59.6, 60.9;

56.0, 56.2, 59.6;

59.7;

56.0, 59.7;

3.485 59.5;

3.477 55.4, 55.9,

3.481 59.7;

3.477 55.6, 56.0, 56.1, 56.3;

3.480 56.4, 59.2, 60.9, 61.8;

3.484 59.7, 59.9;

3.479 56.5, 60.0;

3.483 59.7, 59.9;

3.478 56.4, 59.2, 60.9, 61.7;

3.483 59.7, 59.9;

3.477 55.7, 56.3, 59.6, 59.9;

59.5;

3.476 59.6, 61.1;

60.8;

60.2, 61.2;

167

168
substitution
of
A

the

at

methine

pattern

can

in

methoxy
C-6,

C - 6 or

be

aryl

used

ring A .

C-7

and

C-8

(7.2

of

presence

of

8-C-prenyl

of

e.g.

pattern
ppm

of

ring A as

5,7,-dihydroxy-8-

methoxyl
shift

shifts

groups

difference

The

and

C-8

in

pattern
in

of

C-6

3.5

having

are

two

5-methoxy,

of

ring

system

3.453

of

and

and

ring-

3.476

give

rise

to

presence
possessing

absorbs
an

[173].
because

and

3.454

C-5,

similar

C-8

at

5,7-dihydroxy-8-methoxy

7 and

C-10. These absorb

152.7

differ

and

chemical

especially

113.0

shifts

compounds

in

at

of

are
and

[190]

94.20.1

substitution

absorption

Several

flavones

linked

to

and

at

[173]

pattern

chemical

98.8

for

such

NMR

spectroscopy

related

of

carbon

affected

however

the

far,

flavonoid

have

been

been

rest

nonsulphated

with
of

is

to

respect
13

the

C
a

in

(or

novel

Such

patuletin
most

(3.414)

and

3-sulphate
of

the

patuletin

(3.521).

signals
(3.425)

at

The
the

except

in

an

important

3.6)
to

the

flavone
3.4

tool

for

[167,201-203]
site

of

the

,
are

for

mainly

close

resemblance

cases

studied

or

flavonol.
13

therefore

the

all

positions

the

In

Flavone

C shielding

C NMR s p e c t r u m
same

variation
T h e 13 C
structure

because

sulphation

shows

form,

flavonoids

flavonol sulphates will be presented

here.
B a r r o n .e_L _al_. [ 1 8 1 ] c h a r a c t e r i z e d
quercetin-3-sulphate
13

display

whereas

difference

conjugated

sulphate).

spectrum

in section

C-

clear.

occur

compound.

either

discussed

be

(Table

hydroxy

moiety

already

found

of

SULPHATES

bisulphate

compounds

resonances

otherwise

with

the

has

these

Table

shift

designated as Flavonoid Sulphates. The distribution, structural

their identification h a v e been r e v i e w e d b y Harborne [ 2 0 0 ] .

elucidation

in

i n c a s e of f o r m e r

reason

well

flavonols

inorganic

3.482

the

ppm

The

FLAVONOID

and

to

119.6

i s not

and

substitution

respect

later.

resonances

3.7

covalently

with

140.4

case

of t h e s e

3.448

6,7-methylenedioxy

reports

and

at

ppm i n b r o u s s o f l a v o n o l A (3.505)

[198].

3.547

and

oxygenation

1.9

substitution

in

shift
ring-

of

trisubstituted

having

represents

chemical
shift

chemical

C-6 resonance

these

of

(3.507)

the

[186,187].

There

at

of

6" , 6 " - d i m e t h y l p y r a n o - ( 2 " , 3 " : 7 , 6 )

while

alter

chemical

the

field

substituent

[192,193]

not
the

differentiation

also

between

higher

does

therefore,

5,7-dihydroxy-6-methoxy-

positions,

5,7-dihydroxy-6-methoxy
ppm

the

Melibentin

ppm)

C - 6 absorbs at

C-8 position

carbon,

for

For

substitution.

magnitude
The

either

unsubstituted

as

signals

of

these

noted
of

for

carbons

so

sulphate
behaviour
(3.520)
compounds
quercetin
2,3,4,10

131..1 157,.0
98..6 164,.3

156..6 132.,0 178.,0 152 .5

155.,7 132.,6 177. 6

155..7 132..2 177,.8 152 .3

155..8 133..1 177..8 161 .2

146..2

155..6 133.1

155,.6 133..3 177..7 161 .4

154 .9 132,.5

156,.0 132,.8 177,.9 161 .2

3..521

3.,522

3..523

3,.524

3,.525

3,.526

3,.527

3,.528

3,.529

3,.530

3,.531

3,.532

161 .2

176.,5 160 .0

178..2 159 .9

177..7 161 .5

177.,8 159 .8

OMe:

158 .9

158 .7

159 .5

97,.6

102,.2
92.2

97.5

97.A

96.6

96.4

97.4

97.5

96.9

93.5

93.8

93.5

93.6

93.3

97.7

93.4

97.5

C-8

C-10

C-l'

C-2'

C-3'

C-5*

C-6'

159 .4 115..5 129 .6

C-4'

181

181

168

201

168

Ref

115,.0

168
153 .2 112.0 126 .3 168

3.528 55.8;

3.532 55.3, 56.0.

156.,3 105. 2 122. 7 131,.0 113.6 161 .0 113,.6 131 .0 203

155..9 106..7 124. 7 129..8 119.2 155 .6 119..2 129 .8 168

r
106..7 126. 3 1 1 7 . .3 148.4 143 .6 121..6 120 .9 168
\ > '>.
156.,5 106.,0 123.,0 120,.8 140.1 152 .2 116,.6 126 .8 202

156,.2 106..9 122. 2 121..3 141.9

155..0 105..4 127. 8 115,.9 148.7 142 .1 121..8 118 .2 168

154..2 105..4 127.8 119..8 115.0

150 .2 111,.5 121 .7 168

104..2 126. 5 117.7 148.1 143 .3 121,.6 120 .6 201

156,.6 106..4 122. 9 115..3 146.1

156.2

156.1

104.,0 123. 1 121.,6 140.5 152 .0 116..8 126 .9 201

157,.4 104.1 123. 1 121..6 140.5 152 .0 116,.8 126 .9 201

151..3 104.,5 121. 6 115.,1 144.7 148 .3 115..9 121 .6

155..2 105..4 121. 3 114..9 145.8 149 .5 116.1 120 .5

156.( 104..1 121. 6 115.,1 144.7 148 .3 115..9 121 .6

156..1 103..1 122. 6 122..2 140.8 151 .2 117..2 124.9

155..2 105..0 121. 0 129..6 115.5

C-9

3.525 55.6;

165 .0

159 .9

102,.3 159 .6

102,.3 159 .3

102,.4 159 .4

100,.9

100,.9

101,.9

98,.6 164 .1

131,.4 156 .2

101..4 159,.0

3.523 59.8;

159 .0

3.521 60.0;

177,.6

155..6 133..5 173..2 160.7

146..3

155..4 133..1 178..0 160 .9

148..2 136.9

Other signals:

98..4 163,.9

156..6 132.,3 177.,7 161 .3

3..520

98..2 163 .9

3..519

C-7

159 .7 101,.3 159 .2

146..1 135..9 175.,9 160 .7

147..6 136..2 176.3

C-6

C-5

C-4

3..517

C-2 C-3

3..518

Str.No. Solv.

Carbon-13 NMR chemical shifts of flavonol sulphates3

TABLE 3.6

169

170

(3.515)

broussoflavonol C
tetramethyl ether

(3.516)

broussoflavonol D
tetramethyl ether

R'

OR
OR

(3.517)
(3.519)
(3.526)
(3.527)

OR

(3.518)
(3.524)

R'=R =H
2
R'=OH,R =H
2
R ' = H , R = S 0 3K
2
R ' = O H , R = S 0 3K

OR

R'=R =H,R =S033

2
R'=R =S03,R =H

OR

OH

(3.520) R ' = R = R 3 = H
2
3
(3.521) R'=0Me,R =R =H
f
2
3
(3.522) R = R = H , R = S O ;
2
3
( 3 . 5 2 3 ) R ' = O M e fR = H fR = S 0 3

(3.525)
(3.528)
(3.529)
(3.530)
(3.531)
(3.532)

R ' = S 0 3K , R = O H , R = M e
2
3
R ' = R = O S 0 3K , R = M e
,
3
2
R = R = S 0 3K , R = H
3
2
R ' = R = S 0 3K t R = O H
2
3
R = S 0 3K , R = O S 0 3K t R = H
2
3
R=R =R =H

171
and

6'.

shifts
of

The

downfield

9 . 6 0 . 1 and

sulphation

shifts

of

orbital
The

O H at

C-2 a n d

system

C-10

upfield

due

and

chemical

C-3

to

C-6'

shift
are

If
as

noted

for

resonances

phenolic

hydroxyl

and

downfield

204].

in

along

resonances

with

quercetin,
1

C-3 ,
and
as

shown

shifts
C

group

is

as

shifts

(para

by

of t h e

by

Ragan

'anthocyanins'
cyclic
by

the

Hrazdina

[205]

In

ppm
13

3.522-3.525
and

indicate

C
C-3
and

155.4-

sulphation

ortho

4.9

3.6
are

noted

and

the

ppm

of t h e

induced

shifts

as

C-6',+1.6
of s u l p h a t e

pattern

and

4'

positions.

can

be

very

of
The

well

having sulphation

used
other

of

carbon

[168,201,

ppm

upfield

C - 2 ' , C - 4 ' . and

: C-4',-4.3

presence

related

ipso

carbons

and
ppm,

para

e x h i b i t s 4.2

C - 2 ' , +2.0,

C-2

sulphation

for

related

the

155.4-156.6

general,

para

sulphation

The

and

displacement

and
and

[204]

the

at

4'-position

(ipso

effect);

(meta

effect);

group

at

induced

sulphation
in
than

other
shifts

induced

calculating
C-3

the

position.

ANTHOCYANIDINS

chromophoric

chemistry
and

the

Similar

position,

ipso,

6.9,

3'

h a v i n g no k e t o

ring C . The

C-3

C-3

effect);

3.8

are

whereas

exhibits similar

at

at

146.1-148.2

the

of a f l a v o n o i d s u l p h a t e

These

1.0-1.6

146.1-148.2

which

(3.518),

[203].

ring

C-3

affected.

(3.523)

effect)

flavonols

ranges

located

ortho

The

(ortho

sulphation

noted

not

position;
3.5),

shift

of

at

of

residue.

moiety.

exhibits upfield

downfield

aromatic

presence

and

C-2

particularly

3,4'-disulphate

of

compounds.

for

normal

respectively.

C-l',+4.5

positions

3-hydroxy

shift

(section

get

C - 5 , +6.0

upfield

3-0-sulphate
occur

tetra-sulphated

flavonol

group
at

+3.2,

by

compounds

chemical

quercetin-3'-sulphate

C-6'
in

and

of t h e

displacement

shift

the

(3.532)

The

the

in

at

tri-

flavonol

aromatic

these

by

difference

upfield

indicative

to an i n c o m p l e t e o v e r l a p

created

respective

characteristic

appear

unusual

and
are

ether

sulphate

resonance

in

resonance

group

are

C-3

The

C-3

C-4 resonances

sulphate

di-,

group

the

attributed

hinderance

induced

156.6

C-3 h y d r o x y l

of

C - 2 and

in k a e m p f e r o l - 3 - 0 - s u l p h a t e - 7 , 4 ' - d i m e t h y l

[168,201-203].

at

been

to

3.528-3.532
ppm

the

position.

resonances

alteration

other

of

steric

also noted

and

(3.40.1)

C-4 h a v e

positions relative

position
[205]

of

the

shift

1.90.1 ppm

group
and

I a c o b u c c i and

aglycones
but

of

possessing

distribution
Sweeny

the

glycosidic

conjugated

has

been

pigments

charged

recently

heteroreviewed

[206].

13
To
nidins,

the

namely,

best

of our

knowledge,

C NMR d a t a

for

o n l y two

5,7-dihydroxy-4' -methoxy-6,8-dimethylanthocyanidin

anthocya(3.533)

M+H

3.533

3.534

C-3

(3.533)

C-4

C-5

C-6

161.3 146.3

C-8

C-9

168.8

5,7-dihydroxy-4'-methoxy-6,8dimethylanthocyanidin

113.4

116.9

C-10

(3.534)

94.8 156.3

182.1 105.7 152.2

C-7

OMe: 3. 533 55.4

133.9 157.9 103.1

157.2 100.4 131.9 157.2 115.1

C-2

Other Signals: Me: 3. 533 9 .5 , 7. 7;

Solv.

Str.No.

Carbon-13 NMR Chemical Shifts of Anthocyanidins3

TABLE 3.7

cyanidin

121.7

123.3

C-l 1

117.7

127.2

C-2'

147.2

114.6

C-3'

155.0

161.6

C-4'

112.2

114.6

C-5'

127.1 208

127.2 207

C-6' Ref.

172

173
and

cyanidin

skeletal

(3.534)

resonances
13 C

The
hanced

by

range

The

C-4 absorb
The

the

oxy

and

shifts

which

this

aryl

94.8

chapter.

were

have

been

of a r o m a t i c

analysed

Perhaps

r i n g C at

aryl

carbons
to

was

group

other

C-3

C-6

insensitive
by

than

as

presence

such

flavones.

of
field

and
The

results

be

long

whereas

is

of

in

C-

methine

ppm

resonances

other

of

en-

experiments

168.8

difference

for

the

among

absorb

at

the

chemical

flavonoids

discussed

charged

o x y g e n of

responsible

for

the

the

obser-

position.

ring

T h e c h e m i c a l s h i f t of
13
exhibit
C shielding pattern

unassigned

reported
13 C s h i e l d i n g d a t a
i n T a b l e 3 . 7 . T h e a b s e n c e of h y d r o -

incorporated

position

to

means
ppm

position,

positively

seems

low

ring A

and

noted

146.3

methine

ppm

All

nuclear

n.O.e.

C-4 resonance

field

C-8

8.3

at

The

low

and

position

at

analysed

at

the

of

ppm.

revealing

para

remaining

similar

133.9

reported.

nature.

by

appears

particularly

greater

resonance

100.4

208]

are

resonance

and

at
thus

C-6

3.533

C-3

carbons. The

ppm,

of

xyl

3.534

161.3

relatively

heterocyclic
vation

at

C-7 resonates

103.1

for

of

hydroxylated

2 and

quite

[207,

polarization transfer
(INEPT)
and a s s i g n e d
1
13
1
decoupling and s e l e c t i v e
C - { H }

type.

in

signals

3.7)

compounds

selective

[208].

all

(Table

in t h e s e

to

the

appearance

of

C-3

resonance

at

ppm.

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