Karimova, and

tupl.icatum'"

<sup>2. G. cornicu- Corydine, Berberine, Sanguinarine, a-Allocryptopine, 30, 31, 47,

Latium isocorydine coptisine chelerythrine, protopine 49, 52</sup>

~-canadineme- chelidonine, ^hohydroxfde, dl-chelidonine,

~-stilopine ^chelirubine methohydroxide

^{3. G. el.egans Corydine, Coptisine} Sanguinarine, ^{Allocryptopine, 10, II, 32} isocorydine, <sup>chelerythrine, protopine

glaucine, chelidonine,

isoboldine, chelirubine,</sup>

O-methyl- dihydrochelery- atheroline ^thrine

^{4. G. fimbrit- Corydine, Coptisine, Sanguinarine, Allocryptopine, 7, 33, 34,}

Zigerum* isocorydine, ^{berberine, chelerythrine, protopine 35} corytuberine, <sup>isocorypalmine chelidonine,

N-methyllind- chelirubine

carpine,

glaufine,

isoboldine,</sup>

glaufidine

_{5. G. fl,avumt Corydine,} Coptisine, Sanguinarine, ^{Allocryptopine, 2, 12, 13,} isocorydine, ^{aurotensine chelerythrine, protopine 16, 17, 19,} corytuberine, ^{chelidonine, 43, 48, 52} magnoflorine, <sup>chelirubine,

bulbocapnine, bocconoline

glaucine,

6,6a-dehydro-

norglaucine,

isoboldine,

O-methyl-

atheroline,

glauvine,

tha1icmidine,</sup>

dicentrine

^{5a. G.} fl.avum ^{Norchelidonine 42}

var. ful.1)W1

^{5b. G. fl.avum Dehydroglau-. Chelidonine 15}

VaX'. ^{leo- cine, glau-}

carpum ^{cine, isocory} dine, O-meth- ylatheroline

_{5c. G. f7,avwn} Dehydroglau- VaX'. vesti- ^{cine, thalic-} tum <sup>midine, cata-

line, corun-

nine, ponte-</sup>

_vedrine

^{14, 25}

_6. G. grandi- ^{Glaucine, Sanguinarine Protopine 11}

_fZorum isoboldine. thalicmidine,

O-methyl- atheroline glauvine

TABLE 1 (continued)

^Alkaloids

Plant species

aporphine protoberberine ^{benzophenan- protopine Literature} thridine

<sup>7. C. "leiocar- Glaucine Aurotensine Protopine 8

pwn</sup>

9. C. oxy"lobwn	^Corydine,	^Coptisine,	Sanguinarine,	^Allocryptopine,	^5,^7
	^glaucine,	berberine,	^chelerythrine,	^protopine	^3,^36^50
	^isobaldine,	^scoulerine,	^chelirubine,
	^dl-isobal-	^aurotensine	^chelilutine
	^dine,^domes-
	^ticine,^pre-
	^dicentrine,
	^O-methyl-
^10.^C.^pu"lch-	^atheroline ^Corydine,			Protopine	18
xrum	^isocorydine,
	^bulbocapnine,
	^N-methyllind-
^II.^C.^serpieri	^carpine ^Isocorydine,	Aurotensine		Protopine	50
^12.^C.^squami-	^glauvine ^Corydine	Coptisine,	Sanguinarine,	Allocryptopine,	37, 52
^gerwn ^13.^C.^vUeUi-	Corydine,	^berberine ^Tetrahydro-	^chelerythrine ^Sanguinarine,	^protopine ^Allocryptopine,	18, 38
num	^isocorydine,	^palmatine	^chelerythrine,	^protopine,
	^corytuberine,		^chelirubine	^muramine
	^bulbocapnine,
	^glaucine,
	^dicentrine

^{8. C. "lutewn Glaucine Sanguinarine}

*In additon to the bases mentioned, the benzylisoquinoline alkaloids N-methylcoclaur1ne and reticuline have been isolated from this species.

t The morphinan alkaloid sinoacutine has also been isolated from C. con tor tup"licatwn, and salutaridine and O-methylflavinantine from C. f"lavwn.
The tetrasubstituted aporphine alkaloid glaufine (IX), containing three hydroxy groups and one methoxy group, has been isolated from C. firribriUigerwn [20]. According to its UV spectrum, glaufine is a 1,2,10,11-substituted aporphine alkaloid [21]. On the basis of the appearance of the NMR signal of the methoxy group in a strong field and the production by its methylation of N-methyllindcarpine (XII) and isocorydine (XIV), structure (IX) has been estab­ lished for glaufine

^H3_H^{CO- "}_O^{'-. I} _g^N_?^{-CHa ,\}_R^(;0

_'O^{"'- I}_w^N-CH3

HO :? . R20 ~ I

HO '''_ I HaCO "'-

IX XIt. R.,=R.2=H

XPJ. R"CHs; R2=H
Two new pentasubstituted aporphine alkaloids have been isolated from plants of the genus G"lauciwn - cataline (XVII) and glaufine (XVI), each of which contains a hydroxy group in a orientation at C4• This was established on the basis of a study of the NMR spectra of the bases themselves and of their acetyl derivative. An analysis of literature information shows that when the hydroxyl has the a orientation the geminal proton at C4 gives a signal in the

4.43-4.47 region in the form of a poorly resolved triplet with a half-width of 5-6 Hz [22], while in the case of the a orientation of the hydroxy group it appears in the form of a quad­

ruplet in the 4.93-5.00 ppm region (J1 = 10 Hz, J2 = 5.5-7 Hz) [23].

In these alkaloids, the aromatic proton at Cs gives a signal in a weaker field than in the aporphines without a substituent in position 4 [24]. The catalytic hydrogenation of (XVII) with palladium on carbon gave glaucine, which confirms the 1,2,9,10-substituted struc­ ture of cataline [25].

co : N-.cH~

_{HSC0ziIH ""OH}

^H3

XVI

H3CO ""- II DCl-i3

):VII

In contrast to cataline, glaufidine is a 1,2,lO,11-substituted aporphine [26]. Four oxo­

ⁱⁿ

aporphine alkaloids have recently been isolated: O-methylatheroline, glauvine, corunnine, and pontevedrine. O-Methylatheroline has been detected five species of GZaucium [3, 9,

10, 13, 15]. The new alkaloid glauvine (XIX) has been isolated from the same plants, its prime source being G. fZavum [13]. There is a report on the formation of glauvine from 0- methylatheroline [13]. These two alkaloids have the same elementary composition and the same substituents, but differ in the locations of the carbonyl group and one methoxy group. In

^{glauvine, the c=o group is present in position 10 and one of the methoxy groups in position 7.}

On thermolysis, O-methylatheroline (XVIII) is converted into glauvine. Corunnine (XX) isolated from G. fZavum var. vestitum is l-hydroxy-2,9,10-trimethoxy-7-oxoaporphine. The oxidation of glaucine chromium trioxide forms a mixture consisting of O-methylatheroline, corunnine, dehydroglaucine, and pontevedrine (XXI). Treatment of (XVIII) with methyl iodide

also forms (XX) [14].

In addition to corunnine, the dioxoaporphine alkaloid pontevedrine (XXI) has been iso­ lated from G. fZavum. The oxidation of cataline (XVII) has given pontevedrine, and the treat­ ment of the latter with a methanolic solution of alkali leads through the benzilic acid (A)

to compound B [27-29]. These facts have enabled structure (XX) with a double bond at 6a-7 and two carbonyl groups at C4 and C5 to be put forward for pontevedrine.

Pontevedrine is the first example of a 4,5-dioxoaporphine isolated from plants.

Another widespread group of bases in plants of the genus GZauaiwn is formed by the benzo­ phenanthridine alkaloids. Sanguinarine and chelerythrine have been isolated from the majority of species [7, 9, 11, 16, 30-38]. A study of the pharmacological properties of these alka­ loids has shown that they possess an antimicrobial action [39, 40] and also increase the in­ traocular pressure and exert a depressive action on the smooth musculature [41]. In recent times, only one new alkaloid belonging to this group of compounds has been found in these plants - norchelidonine (XXII) [12, 42].

The protoberberine alkaloids coptisine and berberine are found in almost all GZauaiwn plants [II, 30, 34, 36, 37, 43]. The methohydroxideof (-)-I3-canadine (XXXVIII) and the methohydroxide (-)-I3-stilopine (XXXVII) are new alkaloids of this group [31]. The represen­ tatives of the other groups of isoquinoline alkaloids are few. They include the protopine alkaloids protopine, allocryptopine, and muramine [18]. The first two alkaloids are found in almost all plants of the family Papaveraceae [41, 44, 45]. Three morphinan alkaloids are known: sinoacutine (XLII) [13,. 46], salutaridine (XLIII [2,4,47]), which are enantiomers, and the methylflavinantine recently isolated from G. fZavum [41. This the first example of the finding of this alkaloid in the family Papaveraceae.

Two benzylisoquinoline alkaloids have been isolated from the plant G. fimbriUigerum:

^{N-methylcoclaurine (XLV) [35] and reticuline (XLVI).}

TABLE·2

Alkaloid

Structural formula


_Literature

I. 6.6a-Dehydtonorglaucine,

<;oHnN04

_{II. Dehydroglaucine,CzIHzsN04•}

mp 133-134·C

15

15, 25

^{TABLE 2 (continued)}

Alkaloid

Structural formula

Literature

Aporphine bases

_~³_~8^., _~

~ ^{Ii N-C}.^l3^l

<sub>I

7</sub>

^{11 -:?" I}

10 ~

9

III. Dornesticine, C19HI9NO", mp

155-1S6°C (ether), [aID +56'

( chloroform)
IV. Isobaldine, CI9H21N04, mp

_{126-127° (methanol),}

[a]D +4So (chloroform)

_{V. Dicentrine, C,n~,N04' mp}

168-169° ~methanoll.

[a]D +620 (chloroform)
VI. Thalicmidine, C;O~SN04' mp

_{191-192° (methanol),}

^{[a Jo +40° (chloroform)}

VII. Predicentrtne, C;o~3N04'

[a]D +97° (ethanol)

VIII. Glaucine, c;IH2SN04, mp

120-121° (ether), [a]D +114°

(ethanol)

_{IX. Glaufine, ClsH19N04'}

[aJD +183° (methanol)

X. Bulbocapnine, C19H19N04, mp 199-200° (ethanol),

[a JD+237° (chloroform)
Xl. Corytuberine, ~9~IN04' mp

240-242°C (decomp •• meth­

anol), (et]D +314°(methanol)
XII. N-Methyllindcarpine, C19H21NO""mp 198-200·C (decomp., methanol),

[aJD +340° (methanol)

<sub>XIII. Corydine, C:zoH2SN04'mp

149-1S0°C (metnanol),</sub>

^{[a10 +204° (c O.S; chloro­}

form)
Rl=OH R2=OCH3

^R9_1O=CH202
RI,9=OH R2,1O=OCH3

RI_2=CH20Z

.R9,!O=OCH3
R1=OH

R2, 9,IO=OCHs

RI,9,IO=OCHa

R2=OH

R1, 2, 9, ]O=OCHs
Rl_2=CH?Oo R1o=OCH; - Rl1=OH
R],u=OH R~,!o=OCH3
_{! R],.10=OCHs}

^{. R2,1I=OH}
36

10. it, 13, 17, 3.5,.

36,5:)
2, 4, 46

9, 1'.), 25

3

3, C.8--18,52

20

3, 4, 18

<sub>I 33, 38, 43

I

!</sub>

I 1'3, 20

<sub>I

I 7. 11. is, 30. 38,</sub>

^{I 47,49}

_I

i

<sub>\ii, 'I -I~e,

ISc, -0~, 3.0 .</sub>

XIV. Isocorydine, Czo~3N04' mp

184-185°C (acetone).

[et]D +19S· (chloroform)

+

XV. Magnoflorine. C;OH2SN04,

mp 249-2S0·C, [a]D +197°

(methanol)

XVI. Glaufidine, C;OH2SNOs•

[et]D +182· (methanol)

XVII. Cataline, C21H2sN0s, mp lS3-184°C, [aJD +166· ( chloroform)

31, 33, 35, 38, 42

43

26

R1, 2,9, IO=OCHs ²⁵

P.=a-OH

^{TABLE 2 (continued)}

_Alkaloid

Structural formula

Literature

_{Oxoapolphine bases}

XVIII. Oe-Methylatheroltne,

CzOH17NOs.mp 223-224°C

_{XIX. Glauvine. CzoHnNOs. mp}

^{210-212°C (methanol)}

₊

XX. Corunnine, ~OH17NOs. mp

255-257°C (ethanol)

3, 9, 10, 13, is

9, 10, 13, 15

14

XXI. Pentevedrine, C,1~19N06. mp 269-271 °C [cruoro­ form - ethanol (1: 1)]

o