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Vol.47. O .4, p 565-580, J u l - A ~ g 984

565

DIMERIC APORPHINOID ALKALOIDS, 11

H E L ~ N E

U I N A U D E A U ,

Labwatoire de Pha-ognosie, FarultC de MCderine et

de

Pha-ie, 87 032 Limoges, France

MICHEL EBOEUF,and ANDRECAVE

Laboratoire

de

Pharmacognosie,

ERA

31

7

C N RS , Faculti de Pharnucie, 9 22 90 Chatenay-Malabry, France

Substan tial progress has been registered du rin g th e past five years in the realm o ft h e

dimeric aporphinoid alkaloids. These classically include the aporphine-ben-

zylisoquinoline dim ers, th e proaporphine-benzylisoquinoline imers, and the hernan-

daline-type alkaloids which are oxidation products of the aporphine-ben-

zylisoquinolines. To this listing m ust now be added novel structural types of dime ric

aporphinoids, such as uskudaramine, which is an aporphine-benzylisoquinoline imer

bonded through carbon-to-carbon linkage, and the bisaporphines, which are dimeric

aporphinoids also connected th rou gh carbon-to-carbon bond ing.

T he present review supplem ents an earlier one that appeared in 197 9. Tw enty-

eigh t dimers were known at tha t tim e; however, additional physical and spectral data

have become available for some of these comp ound s since that tim e, a nd th is informa-

tion is included in the present review. Furthermo re, some

30

new dim ers have been de-

scribed since 19 79 and have been duly included here.

It is important to note that all of the known, naturally occurring dimeric apor-

phino ids have been found in only four plant genera: BerberiJ (Berberidaceae),Hemandia

(Hernandiaceae), Polyalthia (Annonaceae), and Thalictrum (Ranunculaceae).

Th e present review has been organized alon g th e following lines:

1. Additional data on previously reported dimeric aporphinoids (structures

a. physical and spectral data

b. new botanica l sources

New dime ric aporphinoids (structures

29-59)

a. oxygen-bonded

aporphine-benzylisoquinolines

1-28

2 .

i .

i i .

iii.

reticuline-reticuline dimers (thalicarpine type

29-31,

foetidine

reticuline-coclaurine dimers (istanbu lamine

34,

halifaberine-type

35-36)

coclaurine-coclaurine dimers (pakistanine type

37-39,

kalashine

type 40-42, lumipakistanine 43) .

b. oxygen-bonded proaporphine-benzylisoquinolines (pakistanamine type

44-47,

epivaldiberine

48)

c. oxygen-bonded and oxidized

aporphine-benzylisoquinolines

49-51) ,3

and proaporphine-benzylisoquinolines 5 2 )

d . carbon-bonded dimers

type 32-33)

i .

aporphine-benzylisoquinoline

imer (53 )

ii. bisaporphines (54-59)

H. Guinaudeau,

M .

Leboeufand A. Cave, Dimeric

Aporphine-benzylisoquinoline

nd Aporphine-

pavine Alkaloids,J. Na t. Prod.,

42,

33 (1979).

Synthetically derived proaporph ine-aporphines and bisaporphines w ith unlikely biogenetic linkages

( v i z .

reference 5 , 11 , 27, a nd 41 ) have not been taken into account in the present review.

3Th e known oxidized

aporphine-benzylisoquinoline

imers hernanda line, hernandalinol, thaliadine,

and de hydrothaliadine have been reported in A porphine Alkaloids, Lloydia, 38, 275 (1 975), andJ. Nat .

Prod.,

42,

25 (1979).

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Within each section, the material has been arranged in an ascending order

of

sub-

stitu tion patte rn. T he nu mb ering system is according to the accepted rules.

a f b

14'

A

131

11

10

9

RN

2

a b

14'

13'

0

Unless stated otherwise, uv (nm, log

E)

and cd

(A

nm ) spectra were obtained in

E t O H or M eOH . N m r spectra are in CDCI,, chemical shifts are in ppm on the 6 scale,

and the coupling constants are in Hz. Values with identical superscripts are inter-

changeable. r frequencies are in c m- . M elting p oints are in degrees centigrade and are

uncorrected.

TABLE

.

Additional Physical and Spectral Data on Previously Reported Dimeric Aporphinoids

23 Pakistanine C3,H,,N206 608 .28 86

cd:

+

17.6 (310) . +3 2.0 (274) , -52.9 (244), +8 0.1 (21 2) (17)

24

1-0-Methylpakistanine C,,H42N,O6 622 .304 3

cd: + 12.8 (290), -61.2 (2411, +2 4. 7 (220)

(18)

25 1,lO-Di-0-Methylpakistanine C39H44N206 63 6.3 199

cd: + 14 .5 (277), -76 .1 (240), +66 .6 (21 2) (18)

26 Pakistanamine' C38H42N206 622 .30 43

mp : 93-94 (19)

[a] : $135(c= 0 .5 , MeOH) (19)

cd: +7.7 (278) ,

4.8

(248),

+

15.0 (232), + 6. 6 (218) (19)

T h e decoupling experiments and N OED S studies of the 6a -H and 7-H were given. The

stereochemistry at th e C-13 proaporphine spiro-centre is the same as in berbivaldine 44

TABLE

.

Known Na tural Dimeric A porphinoids Reisolated from N ew Sources

5

6

10

15

16

18

21

Tha lipine C,9H44N,O, 668 .30 97

Sources: Thalictrum minus (6)

Thalmelat ine C40H 46N,08 682.3254

Sources:

Thalirtrum minus

(6)

Thalicarpine (Thaliblastine) C4,H4,N,08 696.34 10

Sources: Thalictrum alpinurn (48)

Thalactrurn rmlutum (46)

Thalfrtrum

woiutum

(46)

Tha/irtrumfoliosum(4)

Thalirtrumminus 6,25,31,37)

Thalictrum rwolutum (46)

Thalictrum minus var. MlCrOphylhm ( 2 )

Thalirtrum minus

var.

microphjflum (2)

Thalirtrum minus var. microphyllum

( 2 )

Thaliadanine C,,H,,N,09 71 2.3 35 9

Sources:

Adiantifoline C4,H,,N,09 726 .35 16

Sources:

Thalmelatidine C4,H 4,N,0 ,, 740.33 09

Sources:

Thalirevoiine C4 0H 46 N2 0s 682.3254

Sources: Thafzrtrumrevofutum(46)

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567

23

Pakistanine

Sources:

Berberrs calliobottys ( 2 0 )

Berberis empetrifolia(7 ,9 ,10)

Berberis ortbobottys (16-18)

24

1-0-methylpakistanine

Sources:

Berberis cailiobottys ( 2 0 )

Berberis ortbobottys ( 1 6 , 1 7 )

Synthesis ( 1 8 )

25 1,lO-Di-0-mechylpakistanine

Sources: Synthesis

( 1 8 )

26

Pakistanamine

Sources:

Berberis cailiobottys ( 2 0 )

Berberis empetrifolia ( 1 2 )

Berberis julia nae ( 2 6 )

Berberis wthobottys (16-18)

Berberis valdiviana

(

1 2 )

The biosynthesis of thalicarpine has been extensively studied ( 3 , 31,37). Ow ing to its cytotoxic and

antitu m or activities (thalicarp ine= thaliblastine ), a num ber

of

pharmacological

(1 ,2 1 ,22 ,28 ,30 ,32 ,34 ,

35,39,40,42-44)

and toxicological

(21 ,22 ,33 ,36 ,45)

studies have been published. An hplc m ethod

for

the determination

of

thalicarpine an d derivatives has been reported

( 3 8 ) .

TABLE.

Completely New Dimeric Aporphinoids

29 Nocthalicarpine C4&6N20, 682.3254

[a D: +

108 ( c = 0 . 2 5 ,

MeOH)

( 4 7 )

UV:

282 (4 .21) , 303sh ( 4 .0 8) ,3 1 4 sh ( 3 . 9 7 ) ( 4 7 )

IR:

PMR: (60MHz) ( 4 7 )

MASS:

Sources: Tbalictrum revolutum ( 4 7 )

(CHCI,)

3002, 2940, 2860, 2840, 2800, 1620, 1602, 1580, 1500, 1465, 1400, 1380,

1360, 1325, 1270, 1170, 1150, 1085, 1005,

880,

850

( 4 7 )

682

( M C ,

0 . 4 ) ,4 9 0 ( 4 ) ,341

1

) , 340 (2) ,

325 ( 2 ) ,

324 ( l ) , 06 ( 6 9 ) , 192 ( l o o ) , 177

( 3 ) ,

176 ( l o ) , 148

5 )

( 4 7 )

6.66' 6.61 *

30 Bursanine C4&,6N,O9

698.3200

[ a ~ : 117

(c=O.

17,

MeOH)

( 1 3 )

U V :

PMR: (200MHz) ( 1 3 )

MASS:

CD:

Sources:

Tbalictrum minus

var.

micropbylium ( 13)

209 (4.8 1) , 221sh (4.7 5) , 283 (4.3 4) , 304sh (4.2 4) , 314 (4.1 9)

( 1 3 )

698

( M + ,

0. ) , 6 9 6 ( 0 . 7 ) ,506 (7) ,4 7 6 ( 4 ) ,369 I ) , 192 (100 )

- 5 . 2 (306 ) , -2 .6 (290 ) , -4 .9 (275 ) , +49 .0 (241) , -11 .0 (214 )

( 1 3 )

( 1 3 )

No t previously repon ed in Dimeric aporphine-benzylisoquinoline and aporphine-pavine al-

kaloids. J.

N a t .

Prod., 42 , 133 (19 79 ).

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[Vol.

4 7 , No. 4

a 8

238

3.75

31

2'-Noradiantifoline C41H48N209 712 .335 9

[ a ) D :

+39 (c= 0.08 , MeOH) (15)

UV:

PMR: (200 MHz) (15)

MASS:

CD:

Sources:

Tbalirtrum minus

var.

m i r r o p b y l l w n

(15)

208 (4.77), 220sh (4.69), 280 (4.31 ), 296sh (4.24), 302sh (4.17), 314 (4.10)

(15)

712 (M+,

0 . 3 ) ,

710

(0.8),

681 (0.6) , 520 (6) , 519 (7) , 490 (3) , 369 (I ) , 192 ( loo ) ,

177

(8)

(15)

-5 .3 (304) , -4 .0 (287) , -5 .9 (272) , +38 .0 (2 4 6 , -16 .0 (213)

(15)

3.90

6.47 OMe

32

Iznikine C40H46N209 69 8.32 00

[ a ) D :

+76 ' (c=0.07 , MeOH) (13)

UV:

PMR: (200MHz) (13)

MASS: 697 (0.3 ), 60 8(0 .8), 50 6(1 .7) , 367 0.8), 92 (100) (13)

CD:

Sources:

Tbalictrumminus

var. mic ropby l l um ( 13)

208 (4.68), 222sh (4 .5 4 , 281 (4.17 ), 301sh (4.03), 312 (3.98)

(13)

-6.6 (305) , -1.3 (285) , -5.3 (273) , $27 .5 (241) , -3.4 (220)

(13)

368

33

Huangshanine C 42 H 5$ J2 09 726 .3503

[ a ] ~ :

12 l o ( c =0 . 4 , M e OH ) ( 29 )

UV: 281 (4.41), 302 (4.20), 312 (4.13) (29)

PMR: (200MHz) (29)

MASS: 72 5, 520, 370, 354 , 206 (10 0) (29)

CD: -4.8 (301) , -4.9 (277) , +2 9.2 (243) (29)

Sources:

Tbalirtrumfaberi

(29)

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et

a l .

:

Dim eric Aporphinoid Alkaloids

569

34

35

36

Istanbulamine C39H44N208 668 .309 7

[CC~D: +60 (c =0.09, MeOH) (13)

UV:

PMR : (20 0M Hz ) (13)

MASS:

C D: -15 .3 (306) , -8 .7 (284), -10 .9 (275 ) , f6 1 . 2 (243) ) -16 .0 (210 ) (13 )

Sources:

Thalirtrum minus vat. microphyllum (

13)

205 (4.87), 225sh (4.75) , 270sh (4.20) , 282 (4.3 4), 304sh (4.15 ), 313 (4.12)

(13)

668 (M +, 0 .2 ) , 666

l ) ,

38 (0 .6) , 608 (0 .3) , 476 (4) , 475 (6) , 369 (0 .4) . 354 ( I ) , 192

(100) (13)

m

.1 Hr

Jo

8.2 H2

Thalifaberine C4 1H 48N 208 696.33 98

[a D:

+ 9 5 ( ~ = 0 . 4 ,MeOH) (29)

UV: 282 (4.36), 3 lOsh (3.98) (29)

PMR : (60 M Hz) (29 )

MASS: 696 (M +,

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47,

No. 4

37

38

39

3.81 3.91

*

OMe

PORVENIRAM INE C36H38N906 594 .2728

[a ~:

4O o(c= 0. l , MeOH) (12)

UV: 225 (4.66), 267sh (4.19), 277 (4.26), 307 (3.90) (12)

PMR: (360MHz) (12)

MASS: 594 (M + , 0.2), 402 (7), 295 (2), 192 (100)

CD: +5 .4 (305) , $8 .2 (274) , -24.0 (244) , +2 2.0 (21 2) (12)

Sources: Berberis empetr oha (12)

(12)

653: 6.55:

CHITRALINE C&38N@, 594.2 728

[a D:

+

1 3 6 ( ~ = 0 . 1 7 ,MeOH) (12)

UV:

PMR: (200MHz) (17)

MASS: 593, 401, 192 ( l oo ) , 177 (17)

CD: +1 2 .3 (310), +14 .0(27 2) , - 52 .7 (244), +3 5 .1(2 15) (17)

Sources:

220sh (4.51) , 268sh (4.03) , 278 (4. lo) , 292sh (3.94) , 304 (3.96)

(17)

Berberis calliobottys (20) , B . empetrifolia (121, B . wthobotryJ (17), B. ualdiuiana (12),

B . iubeliana (20)

696

N O NAME 1-0-ME THY LCH ITRA LINE ) C3,H,,N@6 608 .28 86

{ a ] ~ :

29 ( c=0 .4 , MeOH) (12)

UV:

PMR: (360MHz) (12)

MASS: 608

(M+,

.2) , 416 (4) , 206 ( lo ) , 192 (100) (12)

CD: + 2 .6 (304) , +7 .2 (275) , -33.0 (239) , +27 .0 (210) (12)

Sources: Synthesis (12)

210 (4.60) , 224 (4.54) , 267sh (4.04) , 278 (4.1 7) , 304 (3.97) (12)

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Dim eric Aporph inoid Alkaloids

57

1

6.53

6.97

M

8.10

40 KHYBERINE C36H38N206 594.2728

MP: 145-147 (20)

[UlD:

- 4 7 ( ~ = 0 . 0 6 ,MeOH) (12)

UV:

PMR: (20 0M Hz ) (20)

MASS: 593, 403, 402, 296, 192 ( l oo ) , 107 (20)

CD:

Sources:

Berberis

calliobotrys ( 2 0 )

220sh (4.53) , 264sh (3.97) , 272 (4.02) , 292sh (3.80) , 304 (3 .70) (20)

+3 .2 (308), +3 .1(2 92 ) , +3 .4 (275), - 54 .0 (234), +3 6 .0 (214)

(20)

Synthesis (12)

889 Jo

8.7 HZ

6.69

j08hz

J o a H z

869d 7.00

d

41 KA LAS HINE C37H4,3NZO6 60 8.2 88 6

UV: 220 (4.5 4) , 272 (4.04 ) , 290sh (3.7 4) , 304 (3.70 ) (18)

PMR: (200MHz) (18)

MASS: 607 , 403, 311, 296, 206 (100 ), 107 (18)

CD: +9 .5 (280) , -50.6 (236) , +4 1.0 (214) (18)

Sources: Berberis calliobotrys (20),

8 . mthobotrys

(16,18)

6.56 6.53

2.47

Me

42 1-0-METHYLK ALASHINE C3&42N206 622.3 043

UV: 222 (4.51 ) , 272 (4.0 0) , 302 (3.6 8) (18)

PMR: (20 0M Hz ) (18)

MASS: 620 , 417 , 310, 20 6(10 0), 190 (18)

CD: +6.6 (285) , -5 .5 (260) , -60 .8 (236), +3 7.2 (212) (18)

Sources: Synthesis (16,18)

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857

6 57

o

.7

Hz

43 LUMIPASKISTANINE C38 H42 N2 06 622.3043

MP: 112-114 (19)

[ a ] ~ :

117(c=0 .5 , E tOH) (19)

UV: 220sh (4.87), 282 (4.55) (19)

PMR: (200MHz) (19)

MASS: 621 , 416, 310, 20 6(1 00 ), 190 (19)

Sources: Synthesis (19)

2.49

Jo8BHz

44 BERBIVALDINE C36H38N206 594.2728

[a D: + 14Oo(c=0 .4 , MeOH) (12)

UV: 214 (4.72), 231sh (4.63 ), 284 (4.0 3) (12)

PMR: (3 60M Hz ) (12)

MASS:

CD: -0 .5 (302) , +6 .4 (278) , +2 .4 (242), +1 2 (212) (12)

Sources: Berberis vuldivianu (12)

594 (M+ , 4 ) , 593 (5) , 402 ( 4 , 192 ( loo ) , 177 (17)

(12)

6.58

6.58

99 br s

45 VALDIBERINE C36H38N206 594.2 728

[ a ] ~ :9 l0 (c =O .4 , MeOH) (12)

UV: 212 (4.71), 231 sh(4 .57) , 284 (4.02) (12)

PMR: (360MHz) (12)

MASS:

CD:

Sources:

Berberis valdiviana ( 12)

594 (M +, 0 .2 ) , 402 ( 3 ) , 192 ( lo o) , 177 (34)

-0 .6 (300) , + 10 (277) , +5 .1 (239), + 14 (23 0)

(12)

(12)

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573

654 650

46

VALDIVIANINE C37 H4 0N2 06 608 .2886

{a]D: +

120

(c=O.2, Me OH ) (12)

UV: 214 (4.74) , 232sh (4.7 2) , 282 (4.1 2) (12)

PMR: (360MHz) (12)

MASS:

CD:

Sources: Berberis empetriflia (12) , B . valdiviana (12)

6 0 8 ( M + , 0. l ) ,402 (4) ,

401

(9) , 206 (loo), 204 (14)

(12)

-0.7

(300), +8.0 (278) , + 3. 8 (235) .

+

17 .0 (211)

(12)

7 P A T A G O N I N E C 3 7 H 4 f 1 2 0 6 6 0 8 . 2 8 8 6

[CI]D: + 192 (c=0.2, MeOH ) (12)

UV: 204 (4.70) , 231sh (4.50) , 283 (4.01) (12)

PMR: (360MHz) (12)

MASS:

CD: +8 .8(2 79) , $5 .5 (248), +32 .0(230) (12)

Sources: Berberis empetr olia (12) , B . valdiviana (12)

608 (M +, 0 .2 ) , 416 (5) , 398 (4) , 294 (4) , 192 ( lo o) , 177 (24)

(12)

6 5 8

6.48.

48

EPIVALDIBERINE C36H38N206 59 4.2 72 8

[a]D: + 3 1 ( c = 0 . 1 , MeOH) (12)

UV: 210 (4.65) . 232sh (4.4 7) , 284 (3.86) (12)

PMR: (360MHz) (12)

MASS: 593

(0.

l),

402

S),

192

(100)

12)

C D : + 2 . 3

(300),

+3 .7 (277) , -5 .2 (246), +8 .7 (212) (12)

Sources: Berberis valdiviana (12)

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JoBSH 689d

'

6.69

dd

,$

J 2.5 H Z

J09 .7Hz

49

NEOLUMIPAKISTANINE

C26H25N05

PMR: (200MHz) (19)

MASS: 43 1 (M +), 416, 400

(loo),

388, 357, 312 19)

Sources: Synthesis

(19)

E61

7.04 d

50 N O N A M E

C26H27N05

[ a ] ~ :29 (c=0.04 , MeOH) (8)

UV:

217 (4.36), 227 (3.99), 304 (3.84) (8)

P M R : ( 2 0 0 M H z)

(8)

MASS: 433 (M +, 21), 416 310 (4), 204 (100)

(8)

CD:

+ 1.9 (300), $4 .2 (274), -23 (239), positive tail at 210 (8 )

urces: Synthesis (8)

51

J O N M E C29H29N07

UV: 257 ( 5 . 1 3 ~ 70 (5.1 3), 335 (4.49) (29)

PMR: (29)

MASS: 50 1 (29 )

Sources: Synthesis

(29)

[Vol. 4 7 , No. 4

431 .1726

433.1888

503.1936

+Th is value was inadvertently given instead of the more exact 503 (29).

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Guinaudeau et a / . Dimeric A porphinoid Alkaloids

575

4.05

OMe

52 COYHAIQUINE C,6H2,N0, 433.188 8

[ a ] ~ :2 8 ( c= 0 .0 2 , M eO H ) 8)

UV: 210 (4 .44) , 231sh (4 .24 ) , 283 (3 .63)

(8)

P M R : ( 3 6 0 M H z) (8)

MASS:

CD: +5 .2 (270) ,

+

1 .3 (246) , +6 .5 (229) 8)

Sources:

Berberis mpetr olia 8 )

433 (M+ , l oo ) , 432 ( 8 5 ) ,416 (30), 404 ( 5 8 ) ,310 (32) (8)

6.62

JoB .5H r 7.08 d

53 USKUDARA MINE C3,H4,N,O8 668.30 97

[ a ] ~ :84 (c=O. 15 MeOH) (14)

UV:

PMR: (36 0M Hz ) (14)

MASS:

416(0.7) , 192

l oo ) ,

177 (13)

CD: -4 .8 (297), -3 .9 (280), +4 8 (244) , -32 (212) (14)

Sources:

Thalictrum minus

var.

mirrophyllum

(14)

209 (4.78), 221sh (4.73), 286 (4.35 ), 300sh (4.1 8), 312sh (4.06 ) (14)

6 6 8 ( M + , 0. l ) , 667 (0. l ) , 608 (0 .3) , 476 (3 .3) , 461 (1 .21, 460 (2 .6) , 446 (1 .8) ,

(14)

390

OMe

2.34

OH

97

Jo

a5Hz

5 DESOXYDECAHYDROBECCAPOLINE C,,H,,N,O, 602.2415

MP: 178-182 (23)

lal~: (23)

UV:

PMR: (90M Hz ) (24)

MASS:

Sources: Synthesis (23 ) (24 )

225 (4.59 ), 244sh (4.35), 276 (4.3 5), 304sh (3.98), 328sh (3.76 )

(24)

6 02 ( M + ,

I) ,

601 (12) ,

598

5 ) .

309

( lo) ,

308 (41), 307 (3 8), 305 (14), 294 (16), 292

( lo o) , 290 (16) , 278

(

lo ) , 277 ( 1 6 ~76 (26), 266 (16)

(24)

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Natu ral Products

6.74

6.06

7.77

d

7.25 t

a3nz

55

BISTEPHANINE

MP: 136-140 (23)

ICljD: 0

( 2 3 )

{Vol.

4 7 , No.

4

7.30

1.5

nz

8 . 3 ~ ~

UV:

MASS:

Sources: Synthesis

( 2 3 ) 2 4 )

225 (4.61 ) ,244sh (4.34) , 278 (4.3 2) , 306sh (3.9 4) , 330 (3.6 7)

( 2 4 )

PMR: (90 MHz) ( 2 4 ) ; lso in C6D6 ( 2 3 )

616

( M + ,

l ) , 6 15 ( 3 ) , 614 (6 ) , 308 (36 ) ,307

l oo ) ,

06 (37) ,305 (74) ,293 (13) ,292

( 4 0 ) ,291

(1

, 290 (42 ) ,26 6 ( 9 ) ( 2 4 )

6.06

.98d(wN5

i s n z

7.17

8.3

Hz

56

POLYBECCARINE C ,,Nz06 578.1476

MP:

>280 (24)

UV:

IR: (KBr) 1650 (24)

PMR:

( 2 5 0 M H z ) ( 2 4 )

MASS:

Sources: Polyaltbia caulipWa var. bmarii ( 2 4 )

216 (4.6 6) , 234 (4.7 0) , 248sh (4.6 8) , 273 (4.5 5) , 308 (4.1 7) , 334 (4.0 5) , 406 (4.2 4) ,

425 (4.23);

(HCI)

21 6, 234sh, 2 66 , 280sh, 340, 396, 4701

( 2 4 )

579 (4 0) , 578 ( M f ,

loo),

563 ( 1 5 ) , 548 l l ) , 532

l l ) ,

305 ( 5 ) , 291 (1 2) , 290

(18),

276 (9) ,275 5 ) ( 2 4 )

5/21/2018 np50034a001

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Jul-Aug

1984

Guinaudeau e t a / .: Dimeric Aporphinoid Alkaloids

577

6.70 5.91

7.70

6.70 5.91

7.70

57 BECCAPOLINE Cj7H24N207 608.1582

MP: >280 ( 2 3 )

UV:

IR: (KBr)

1650

( 2 3 )

PMR: (CDCIj/CD,OD, 250 MHz) ( 2 3 ) ;also in TFA ( 2 4 )

MASS:

Sources:

218sh ( 4 .5 2) , 231 (4 .6 3) ,250sh (4 .5 3) , 79 (4 .40) , 310 (4 .01 ) , 366sh (4 .07 ) ,4 28 ( 4 . 2 2 ) ,

440 (4 .21 ) ; (HCI) 223sh, 234, 26 5, 279 , 339, 384, 4861

( 2 3 )

6 09 ( 4 0 ) ,608

( M f ,

l o o ) , 5 94 ( 1 7 ) ,578 (7 ) ,5 62 ( 7 ) ,305

( 3 ) ,

304 (3 ) ,291 (4 ) , 90

( 1 3 ) ,

276 (2 ) ,260 ( 2 ) ( 2 4 )

Poiyaithia cauiifira

var.

beccarii ( 2 3 ) 2 4 )

58

BECCAPOLINIUM Cj,H,,N,O, 623.1816

MP: 250 (dec) (24 )

UV:

IR: (KBr) 1650 ( 2 3 )

PMR: ( 4 0 0 M H z ) ( 2 3 )

MASS:

Sources:

218 (4 .7 1) , 235sh (4 .6 7) . 262 (4 .5 7) , 280sh (4 .5 0) , 338sh (3 .9 7) , 384 (4 .1 8) , 440sh

( 4 . 0 5 ) .480sh (3 .90 ) (23 )

625 (75 ) ,6 1 2 ( 2 6 ) ,611

l o o ) ,

597 (16 ) , 582 ( 15 ) , 316 ( 3 0 ) , 308 ( l l ) ,302 (20 ) , 301

( 2 3 ) ,2 86 ( 2 0 ) ( 2 4 )

Poiyaithia cauiafia var. beccarii ( 2 3 ) 2 4 )

5/21/2018 np50034a001

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578

Journal of Natural Products

[Vol.

47,

N o . 4

7.78

t

J 8 H r

59 BECCAPOLYDIONE C3,HZ2N209 638.1324

MP: >280 24)

U V :

IR:

(KBr) 1665, 1650 24)

PMR: 250MHz) 24)

MASS:

305 29), 90

25)

24)

Sources: Polyalthia

caulifia

var. beccarii

24)

218sh 4.53),

24

4.70),50 4.67~76 4.47),

14

4.19),25sh 4.19),70sh 4.02),

438 4.29);

(HCI)

220, 45, 57sh, 90,

25,

384, 641

24)

639 43), 38 M + , loo), 624 36), 97 18), 37 32), 35 32),308 30), 07 21),

a.

4.09

OMe

TABLE

.

Calculated Molecular W eigh ts

of

N ew Dimeric Aporphinoids

431.1726 C26H25N05 594.2728 C36H38N206

Neolumipakistanine 49 Porveniramine

37

Chitraline 38

433.1888 C26H27N0> Khyberine 40

N oname 50 Berbivaldine 44

Coyhaiquine

52

Valdiberine

45

Epivaldiberine 48

C29H29N0?

602.24 5 C3?H34N2 6

503.1936

N oname 51

Desoxydecahydrobeccapoline 54

578.1476 C36H22N206

Polybeccarine

56

608.1582

C37H24N207

Beccapoline

57

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Jul-Aug 1984 Guinaudeau et al . Dimeric A porphinoid Alkaloids 579

TABLE .

Contrnued

608.2886

C37H40N206

1-0-Methylchitraline

39

Kalashine 4 1

Valdivianine

46

Patagonine 47

616.2571 C38H36N206

Bistephanine

55

622.3043 C38H42N206

1-0-Methylkalashine 42

Lumipakistanine 4 3

623.1816

C38H27N207

Beccapolinium 58

638.1324

C37H22N209

Beccapolydione 59

668.3097

C39H44N208

Istanbulamine

34

Uskudaramine

5 3

682.3254

C40H46N208

Northalicarpine

29

696.3398 c4 l H 4 S N 2 0 8

Thalifaberine 35

698.3200 C40H46N209

Bursanine

30

Iznikine 32

7 10 . 319 1 C41H46N209

Thalifabine

36

712.3359

41H4SN209

2-Noradiantifoline

31

726.3503 C42H>0N209

Huangshanine

33

TABLE.

Names an d Synonyms of Dim eric Aporphino ids Cited in This Review

Adiantifoline

16 za

Beccapoline 57

na

Beccapolinium

58

n a

Beccapolydione 59 na

Berbivaldine 44

na

Bistephanine

55 na

Bursanine 30

na

Chitraline

38

n a

Coyhaiquine 52 n a

Desoxydecahydrobeccapoline

54

na

1,lO-Di-0-methylpakistanine 25

sd

Epivaldiberine

48

na

Huangshanine

33 na

Istanbulamine 34 na

Iznikine 32 na

Kalashine

41

na

Khyberine 40

nu

Lumipakistanine 4 3

na

1-0-Methylchitraline

39

na

1-0-Methylkalashine 42 na

1-0-Methylpakistanine 24 sd, za

Neolumipakistanine 4 9 na

2-Noradiantifoline 31 na

Northalicarpine 29 na

Pakistanamine

26 sd, ia

Pakistanine 23

sd, za

Patagonine 47 na

Polybeccarine 56 n a

Porveniramine

37

na

Thaliadanine 15 ia

Thaliblastine

10

ia

Thalicarpine

10

ia

Thalifaberine 35 na

Thalifabine 36 na

Thalipine

5

ia

Thalirevoline 2 1 za

Thalmelatidine 18 ia

Thalmelatine 6 ia

Uskudaramine 5 3 na

Valdiberine

45

na

Valdivianine

46

na

ia zk no w n dimeric aporphinoid isolated again

n a y new dim eric aporph inoid alkaloid

sd=additional physical and spectral data

LITERATURE CITED

1.

2.

3.

2

Astardzhieva and

I.

Stoichkov, Onkologiya (Sofia),

16

131 (1979);

Chem.

Abstr.,

9 2 ,

140526a

(1980).

K .H .C. B w r , Dogu,

Seri A , 5 ,

163 (1981).

D.S. Bhakuni and S. Jain, Tetrahedron,

38,

29 (1982).

5/21/2018 np50034a001

16/16

580 Journal of Natural Products [Vol. 4 7 , N o . 4

4 .

5.

6 .

7 .

8.

9 .

10.

11.

12.

13.

14.

15.

16.

17.

18.

19.

20.

21.

22.

23.

24.

25 .

26.

27.

28.

29.

30.

31.

32.

33.

34.

35.

36.

37.

38.

39.

40.

41.

42.

43.

44.

45.

46.

47.

48.

D.S . Bhakuni and R .S. Singh,].

Nat. Prod.,

45, 252 (1982).

L. Castedo, R . Riguera, J . M . Saa, nd R . Suau,

Hetwoiycles,

6 , 677 (1977).

K .H . Dutchevska, B. Dimov,

V .

Khristov, B . Kuzmanov, and

L.

Evstatieva,

Planta Med..

45,

39

(1982).

V .

Fajardo,

V .

Elango, B.K. Cassels, and M. Shamma,

Tetrahedron

Lett. 23,

39 (1982).

V .

Fajardo, H . Guinaudeau ,

V .

Elango, and

M .

Shamma,].

Chem.

Sw..

Chem. Commun.,

1350

(1982).

V .

Fajardo, A. Leon, M .C. Loncharic, V . Elango,

M .

Sharnrna, and B .K . Cassels,

Bol.

Sw.

Chil.

Quim. , 2 7 ,

159 (1982).

V .

Fajardo, C. Prats, and

M .

Garrido,

Contrib.

Cient.

Tecnol.

(Santiago), 11 61 (1981) ;

Chem.

Abstr. , 9 7 ,

36122h (198 2).

M . Gerecke, R . B orer, and A. Brossi,

Helu. Chim. Acta, 58,

185 (1975).

H . Guinaudeau,

V.

Elango, M. Shamma, and

V.

Fajardo,

j. hem.

Sw.,

hem. Commun..

1122

(1982);

H.

Guinaudeau and M. Shamrna, unpublished results.

H . Guinaudeau, A.J . Freyer, R .D . M inard, M. Sharnrna, and K.H .C. B qe r,

Tetrahedron

Lett.

23,

2523 (1982).

H . Guinaudeau, A.J. Freyer, R.D . Minard, M . Shamma, and K.H .C . Bayx,].

Org. Chem., 4 7 ,

5406 (1982).

H . Guinaudeau, M. Shamma, and K.H .C . Bqer,] .

Na t. Prod. , 45,

505 (1982).

S.F. H ussain, L. Khan , K .K . Sadozai, and M. Shamma,].

Na t. Prod. , 44,

274 (1981).

S.F. Hussain, L. Khan, and M. Shamrna,

Heterocycles, 15,

191 (1981).

S.F. Hussain and M. Shamma,

Tetrahedron

Lett.,

2 1 ,

33 15 (198 0).

S.F. Hussain, M .T. Siddiqui, G . Manikum ar, and M. Shamrna,

TetrahedronLett., 21,

723 (1980).

S.F. Hussain, M.T. Siddiqui, M.T. Manikumar, and M. Shamma,

Tetrahedron

Lett..

2 1 ,

4573

(1980).

M. Ilarionova,

Dokl.

Bolg. Akad . Na uk,

34,

25 (1981).

M . Ilarionova, K . Maneva, and D . Todorov, Dokl.

Boig. Akad . N au k, 33,

7 19 (1980).

A, Jossang, M. Leboeuf, and A. Cave,

Tetrahedron Lett., 23,

5 147 (198 2).

A. Jossang, M .

Leboeuf

A. C ave, T. Sv en et , and K . Padmawinata,].

Nar. Prod..

47,504 (1984).

V . Kristov, P . Demirey, N . Mollova, and V . Nenov,

Int.

Con/

Chem.

Bioteshnol.

Biol. Act. Nat.

Prod. (Proc.),

3 , 367 (198 1);

C h m . Abstr . ,

9 7 , 984 19u (1982).

D. Kostalova, B. Brazdovicova, and J. Tomko, C h m . Zvesti, 32, 706 (1978);

Chem. Absrr.,

9 1 ,

20853n (1979).

S.M. Kupchan, O. P. Dhingra, U . Ramachandran, and C .K . Kim,].

Org.

Chem., 43 , 105 (1978).

L.L.H. Liao,

Prw. Natl.

Sri.

Counc., Repub.

China,4 , 285 (1980);

Chem. Abstr..

9 3 , 1 9 7 6 5 7 ~

(1980).

L.Z.

Lin, H . Wagner, and

0.

Seligmann,

Planta Med.,

4 9 ,

55

(1983).

K . M aneva,

Probl.

Onko l . ,

7 5 (1979); Cbem.

Abstr.,

9 3 , 142974q (198 0).

N. Marekov and A. Sidjimov,

Tetrahedron

Lett., 2 2 , 23 11 (1 981); and Int. Con/ Cbem.

Biotechnol.

B i d .

Acr.

Nat. Prod.

Pm.), , 4 18 (1981); Chon.

Abstr.,

9 7 , 88762m (1982).

A. Milushev and

I .

Stoichkov, Onkologiya (Sofia), 17, 29 (1980);C h m .

Abstr. ,

9 3 , 1 4 3 0 4 4 ~1980).

I. Mircheva and N . Stoichkova, Probl. Onkol.,

8

45 (1980); Chem.

Abstr . ,

9 5 , 162 132h (1 98 1).

D . Popov and D . Todorov,

Dokl.

Bolg. Akad . Na uk,

33,

437 (1980).

D. Popov and D. Todorov,

Dokl.

olg. Akad . Na uk,

33,

115 1 (198 0).

G .N . Rao, T .E . Palmer, M .W . Balk , G .W . Thompson, and

S.M.

Glaza, Battelle ColumbusT ox-

icology Report, 1981;

Chem. Abrtr., 9 7 ,

865

18n

(1982).

A .

Sidjimov and N . M arekov, Phytwhmirriy,

2 1 ,

87 1 (1982).

M . Sm ellie, M. Corder, and J. P . Rosazza,].

Chromatogr.,

155,

439 (1978) .

J. Scoychkov and A. Miloushev, B i o d . Express,

33 ,

42 (1980).

I.

Stoichkov,

I .

Mircheva, M. Darnyanova, S. Marinova, and

Z .

Astardzhieva,

Probl. Onkoi . . 7

0

(1979);

Cbem. Abstr. , 9 3 ,

1 4 2 9 7 3 ~1980).

K.L . S tuart and A. Callender,

Rev.

La t inoam.

Quim. , 3 ,

19 (1972).

D.

Todorov and

G.

Deliconstantinos,

Onkoloiya

(Sofia),

17,

40 (1980);

Chem. Ab str., 9 3 ,

1 7 3 6 7 6 ~

(1980).

D.

Todorovand

G.

Deliconstantinos,

Dokl.

Bolg. Akad. Nauk.

34

33 (1981).

D.K. Todorov, and G. Deliconstantinos,

Experientia, 38,

57 (1982).

D . Todorov, Kh.

Getov,

M .

Ilarionova, and K. Maneva,

Doki.

olg. Akad . Na uk.

34

45 (198 1).

J. W u, J .L . Beal, W .N . W u , and R .W . Doskotch,] .

Nut. Prod.,

43 , 270 (1980).

W .N . W u, J .L . Bea l, and R .

W .

Doskotch,].

Nut. Prod.,

4 3 ,

567 (1980).

W . N . W u , J . L . Beal, and R . W . Doskotch,].

Nu t. Prod.,

43, 372 (1980).

Reseived 24

October 1983