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Isolation and structure of new alkaloid nor-neronine from the bulbs of pancratium longiflorum roxb.
Tetrahedron LetteraNo.37,pp. 4481-4484, 1966. Perguon PresmLtd. Printedin GreatLitain.
ISO.LkTIOPAIiD STRUCTUEB OFAPEWALKATaOIDEOE-EEEOHIHEFRCM TIiB IAILBSOF PIIHCEATIUM L~QI?LORUH %88ngurmi*'
Dopuhentof
ROXB.*
and B.V. Krlehao Eao
Phamaoj,&dhraUnivereity,
Walt&r, India
(Received1 July 1966)
The la& decade end helf bee aeon lntenee activity la the field of chemistry of elk&x&da of the plent family Plaryllldaceae.JWuxutlum low~iflorpcBarb. ie one of the rare awea which haa eecaped attention eo fer. Fmmthe
bulbe of this
plantgrowinginW8ltalr(Indla)
we have
ieolated a new elkeloid which contp;inea phenolic bydroxyl group aud gives neronine with diaeomethane. It io therefore nemed nor-neronine. The minced (fresh) bulbe were extractedwith elcohol, the combined alcoholicextract
partially concentrated,
ehaken with fraebly precipitatedlead bydroxlde (compare ref.11 and filtered. The reaction of the filtrate wee edjueted to pFf6 and the solvent removed under reduced pmeeure with progressivereplacementby water. The pndominantly equeoue residue (pH 6) was extraoted eucceeeively *
These reeulte fomed art of a t&k delivered by the flret author at en InBemotional Colloquium orgmnised by CIYBS,Paris at Iioumeain April-NW, 1964.
**
Pre0ent eddre6s:Department of Chemietxy,Univemity of Delhi, Delhl.7, India.
4481
lo.37
440!2
w$th
patrolaum lthar, ather, CblOrOfOm
and ChlorOfOZIb
aloohol 2:1. The leet two axtrecte gave coloux%eeeneedlae ..p.~8~oo than from
on c~ateIUsetlon frcm chlorofomathenol alcohol (yiald, 0.00%).
!Che main eddition
ohlomfoa
end
of
aqueous extrect wae edjoetad
to Pa 9 bp the
eolid poteeeium carbonata rod extrectedmith end chlorofoa-elcohol 2~1. These two lxtreate
yielded colourlaeeprleme from chloroform-elcohol, m-p. 272-74' (deeomp.) (yield, 0.01%); f0zmil.oCt&7BO4: -105.7' (ebeoluteelcohol).It gave e poeitlw tact I%?; for the mathylanedioxygroup (gPlic ecid-eulphuricecid tart) end fonmed a bydrochlorlde pyridine-aceticenhydrlde It
wp.224-26’
fonned
(decoq.).
with
a dlwetate CZOH2,N06,
r.p.216-18°,[ot); *25.0' (cblomfoxd;
mixed m.p. with
euthentlclgcorine dlecetate from Crinum deflxum2 wee unde-preeead. The properties end compoeitionof the parent compound cud its derlvetlveeestablishedit8 identity e8 lycorine. The eubstrooam.p.2J8-40° (decomp.)mentioned earlier enalyeed for c,7H,7N06'[47;0 +90° (methanol). It gave taste for phanollc (blue violet ferric colour) end methylenedlory groups (I.E. absorptionat 926 om-1 end poeitive gallic acid-eulphuricacid teat). With aodlum ecetate end ecetic enhydride it gave a diecetate,colourleeeneedlae from acetone, C2,H2,N08,m.p.248~50'(decomp.),[ti'l r +20° (chlorofonr).Thaea propartieeindicated *
AU
that
it wae
a
the compound8 whose foraulee are given in this comnmicatlon enalyaed correctly for C, H end N (and -OCH3 wharever this applies).
new
No.37
&kalOld.
Iii01.x. rpectnlm Indicatedthe pwence
of 8
S-l_actonering (strong 8baorptlon at 1710
cm-1 ).
02 the enbatence in methanol with
dlaeomethanne gave
a
ethmeril
product, colourleseprlema from ethyl acetate,
T!redment
m.p.194-96',
3' +154.6' (CblOX'OfOId, rhloh ULtijeed fOT C,$i#06, IO& contained one methoxyl group (mlaro-Zelsel),was not phenolit (negativeferric coloar) end containedhydroxyl function (absorptionat 3520-3510 cm-l in the IA.).
Thle metbl
ether wae extremelyhygmecopic and foned a nethiodlc;e, c18*l~=06*
CE31, .coloufleer, prleme from mathenol,n.p.
265-68' (decomp.). The properties end camposltlonof the methyl ether end lte methiodlde oorreepondto thoee dercribed in the lltrratwe3 for the anaxyllldacwme &l.kaloid neronlne and lte methlodlde. Hence the now phenollc eubbetenoe which give8 the nonphenollcneronine with dimemethene 18 called nolcneronias(eee aleo ref. 4 end 5).
OH
bl R = H, Nor-neronine B = Me, Neronine
4404
No.57
Acknorledaaentr The muthorn thank Dr. B.9.M. Dutt iOr the idantlflc8tlon of the pluit md Prof.T.B.Selrhdri,F.B.8. for hie interest.
1. A. Eunger md 1. Eolohmtoin,
Holv. Chl.8.Aat&
2, 824 (1953). 2.
a.E~Muti
mdB.V.Bm,
1nd.J. Phum.
17, 67 (1955). 3.
&.
Bria,
P.F. Elghet, B.J. Highet md W.C. wildmen,
J. Amer. Chem. Sot. 7&, 2899 (1956). 4. P.W. Jeff@ uid F.L. Wumn,
Cha. k Ind. 468 (1961).
5. P.Y. Jeiia end WA. B8wkerorth,TetznhedronLettea 217 (1963).
ISO.LkTIOPAIiD STRUCTUEB OFAPEWALKATaOIDEOE-EEEOHIHEFRCM TIiB IAILBSOF PIIHCEATIUM L~QI?LORUH %88ngurmi*'
Dopuhentof
ROXB.*
and B.V. Krlehao Eao
Phamaoj,&dhraUnivereity,
Walt&r, India
(Received1 July 1966)
The la& decade end helf bee aeon lntenee activity la the field of chemistry of elk&x&da of the plent family Plaryllldaceae.JWuxutlum low~iflorpcBarb. ie one of the rare awea which haa eecaped attention eo fer. Fmmthe
bulbe of this
plantgrowinginW8ltalr(Indla)
we have
ieolated a new elkeloid which contp;inea phenolic bydroxyl group aud gives neronine with diaeomethane. It io therefore nemed nor-neronine. The minced (fresh) bulbe were extractedwith elcohol, the combined alcoholicextract
partially concentrated,
ehaken with fraebly precipitatedlead bydroxlde (compare ref.11 and filtered. The reaction of the filtrate wee edjueted to pFf6 and the solvent removed under reduced pmeeure with progressivereplacementby water. The pndominantly equeoue residue (pH 6) was extraoted eucceeeively *
These reeulte fomed art of a t&k delivered by the flret author at en InBemotional Colloquium orgmnised by CIYBS,Paris at Iioumeain April-NW, 1964.
**
Pre0ent eddre6s:Department of Chemietxy,Univemity of Delhi, Delhl.7, India.
4481
lo.37
440!2
w$th
patrolaum lthar, ather, CblOrOfOm
and ChlorOfOZIb
aloohol 2:1. The leet two axtrecte gave coloux%eeeneedlae ..p.~8~oo than from
on c~ateIUsetlon frcm chlorofomathenol alcohol (yiald, 0.00%).
!Che main eddition
ohlomfoa
end
of
aqueous extrect wae edjoetad
to Pa 9 bp the
eolid poteeeium carbonata rod extrectedmith end chlorofoa-elcohol 2~1. These two lxtreate
yielded colourlaeeprleme from chloroform-elcohol, m-p. 272-74' (deeomp.) (yield, 0.01%); f0zmil.oCt&7BO4: -105.7' (ebeoluteelcohol).It gave e poeitlw tact I%?; for the mathylanedioxygroup (gPlic ecid-eulphuricecid tart) end fonmed a bydrochlorlde pyridine-aceticenhydrlde It
wp.224-26’
fonned
(decoq.).
with
a dlwetate CZOH2,N06,
r.p.216-18°,[ot); *25.0' (cblomfoxd;
mixed m.p. with
euthentlclgcorine dlecetate from Crinum deflxum2 wee unde-preeead. The properties end compoeitionof the parent compound cud its derlvetlveeestablishedit8 identity e8 lycorine. The eubstrooam.p.2J8-40° (decomp.)mentioned earlier enalyeed for c,7H,7N06'[47;0 +90° (methanol). It gave taste for phanollc (blue violet ferric colour) end methylenedlory groups (I.E. absorptionat 926 om-1 end poeitive gallic acid-eulphuricacid teat). With aodlum ecetate end ecetic enhydride it gave a diecetate,colourleeeneedlae from acetone, C2,H2,N08,m.p.248~50'(decomp.),[ti'l r +20° (chlorofonr).Thaea propartieeindicated *
AU
that
it wae
a
the compound8 whose foraulee are given in this comnmicatlon enalyaed correctly for C, H end N (and -OCH3 wharever this applies).
new
No.37
&kalOld.
Iii01.x. rpectnlm Indicatedthe pwence
of 8
S-l_actonering (strong 8baorptlon at 1710
cm-1 ).
02 the enbatence in methanol with
dlaeomethanne gave
a
ethmeril
product, colourleseprlema from ethyl acetate,
T!redment
m.p.194-96',
3' +154.6' (CblOX'OfOId, rhloh ULtijeed fOT C,$i#06, IO& contained one methoxyl group (mlaro-Zelsel),was not phenolit (negativeferric coloar) end containedhydroxyl function (absorptionat 3520-3510 cm-l in the IA.).
Thle metbl
ether wae extremelyhygmecopic and foned a nethiodlc;e, c18*l~=06*
CE31, .coloufleer, prleme from mathenol,n.p.
265-68' (decomp.). The properties end camposltlonof the methyl ether end lte methiodlde oorreepondto thoee dercribed in the lltrratwe3 for the anaxyllldacwme &l.kaloid neronlne and lte methlodlde. Hence the now phenollc eubbetenoe which give8 the nonphenollcneronine with dimemethene 18 called nolcneronias(eee aleo ref. 4 end 5).
OH
bl R = H, Nor-neronine B = Me, Neronine
4404
No.57
Acknorledaaentr The muthorn thank Dr. B.9.M. Dutt iOr the idantlflc8tlon of the pluit md Prof.T.B.Selrhdri,F.B.8. for hie interest.
1. A. Eunger md 1. Eolohmtoin,
Holv. Chl.8.Aat&
2, 824 (1953). 2.
a.E~Muti
mdB.V.Bm,
1nd.J. Phum.
17, 67 (1955). 3.
&.
Bria,
P.F. Elghet, B.J. Highet md W.C. wildmen,
J. Amer. Chem. Sot. 7&, 2899 (1956). 4. P.W. Jeff@ uid F.L. Wumn,
Cha. k Ind. 468 (1961).
5. P.Y. Jeiia end WA. B8wkerorth,TetznhedronLettea 217 (1963).