<b>The Structure of Argemonine; Identification as (-)N-Methylpavine</b>

Eschscholtzine, a new alkaloid from Eschscholtzia californica, has been shown to be the bismethylenedioxy analogue of 1V-methylpavine (argemonine). The mass spectrometric fragmentation of allcaloids of the pavine type is discussed.Two of us have reported the isolation of a new alkaloid, eschscholtzine, from Eschscholtzia californica Cham.(1) and a mass spectrum* of it showed the molecular formula to be C~~H I~O~N .In the meantime, a fuller mass spectrometric study of eschscholtzine a t Liverpool allowed the correct structure t o be derived which had independently been determined by nuclear magnetic resonance (n.m.r.) and chemical degradation a t Guelph. The mass spectrum of eschscholtzine shows a very small parent peak a t m/e 323 when the hot inlet system was used; however, by direct inlet of the sample, the parent peak increased to about one-third the size of the base peak. In both spectra (hot inlet or direct inlet) only one intense fragment peak appeared a t m/e 188. This behavior is similar to that of the 1-benzylisoquinoline alkaloids (2) but on this basis the only reasonable structure for the fragment ion is (I) which corresponds to m/e 190 and is thus unacceptable.However, the spectra of pavine (IV, R = H) and N-methylpavine (IV, R = Me) parallel that of eschscholtzine in showing a single intense fragment ion a t m/e 190 and one a t m/e 204. These ions are formulated as I1 (R = H) and I1 (R = Me) and their formation can be rationalized as shown below. The nature of the ion from eschscholtzine can now be understood as the aromatic ion (111) and its forination strongly indicated the methylenedioxy analogue (V) of N-methylpavine (IV, R = Me) (argemonine) as the structure of eschscholtzine.The striking similarity of the n.m.r. spectra of argemonine (IV, R = hlIe) (3, 4) and eschscholtzine (V) supported this indication. Both n.m.r. spectra exhibit impressive symmetry and they are largely superiinposable except for the slight shifts described in Table I. The aromatic and N-methyl protons call for no special comiment but the protons of the two methylenedioxy groups appear as a quartet of lines of almost equal intensity: 4.17, 4.21, 4.22, and 4.26 T . The two methylenedioxy groups are thus allnost equivalent but the two protons of the 0-CH2-0 system are not identical as a result of their being in different environments with respect to the aromatic rings. The eschscholtzine molecule is non-planar and may resemble a partly opened hinge. A similar non-equivalence of the methylenedioxy protons has been encountered in the aporphine alkaloids, diceiltrine and bulbocapnine methyl ether (5).

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“…spectra of argemonine (IV, R = hlIe) (3,4) and eschscholtzine (V) supported this indication. Both n.m.r.…”

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confidence: 76%

The Alkaloids of Papaveraceous Plants: Liv. The Structure of Eschscholtzine

Manske¹,

Shin²,

Battersby³

et al. 1965

Can. J. Chem.

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“…UV: (CI04~) (MeOH) 291.5 (3.95) 'H-NMR: (C104")(CD30D) 3.30(s, 6H, N(CH3)2), 3.92 (s, 3H, OCH3), 5.95 (ABq,7= (10) , 190 (67), 189 (16), 188(100), 176(8), 175 (11) , 142( 43 127-128°( Et20) (49) -184.5°(c = 2.20, CHC13) (48) -202°(c= 1.00, MeOH) ( MP: ( ) 285-286°(MeOH) (49) (CKXf) 324-326°( H20) (49) (CKXf) 327-329°(MeOH) (51) [a]lsD: ( ) -212°±3°(c=0.5, MeOH) (…”

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confidence: 99%

“…( -)-amurensine, (-)-amurensinine ( -)-amurensine (-)-amurensinine ( -)-amurensine, (-)-amurensinine ( -)-amurensine, (-)-amurensinine ( -)-amurensine, (-)-amurensinine (-)-amurensine, (-)-amurensinine ( -)-reframidine, (-)-reframine, (-)-reframoline, (-)remrefine ( -)-bisnorargemonine, ( -)-norargemonine, ( -)thalisopavine ( -)-thalidicine, ( -)-thalidine ( -)-argemonine, (-)-argemonine N-metho salt, ( -)eschscholtzidine, (-)-eschscholtzidine N-metho salt, (-)-isonorargemonine, (-)-platycerine (-)-argemonine, (-)-2,3 -methylenedioxy-4,8,9trimethoxypavinane Alphabetical List of Pavine Alkaloids (-)-Argemonine (1) (+ )-Argemonine (2) (-)-Argemonine N-metho salt (3) (-)-Argemonine N-oxide (4) (-)-Bisnorargemonine (7) (-)-Californidine (15) (-)-Cary achine (11) (±)-Caryachine (12) (-)-Caryachine N-metho salt (13) (-)-Eschscholtzidine (8) (+ )-Eschscholtzidine (9) (-)-Eschscholtzidine N-metho salt (10) (-)-Eschscholtzine ( 14) (-)-2-Hydroxy-3,8-dimethoxypavinane (20) (-)-Isonorargemonine (6) (-)-2,3-Methylenedioxy-4,8,9trimethoxypavinane (21) (-)-Munitagine (19) (-)-0-Methylplatycerine (16) (-)-Norargemonine (5) (-)-Platycerine (17) (-)-Platycerine N-metho salt (18) Alphabetical List of Isopavine Alkaloids (-)-Amurensine (29) (-)-Amurensinine (26) (-)-0-Methylthalisopavine (22) (-)-Reframidine (31) (-)-Reframine (27) (-)-Reframoline (30) (-)-Remrefine (28) (-)-Thalidicine (24) (-)-Thalidine (25) (-)-Thalisopavine (23) ACKNOWLEDGMENT This compilation was carried out in conjunction with research supported by grant no. CA-11450 awarded by the National Cancer Insitute, National Institutes of Health, USPHS.…”

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confidence: 99%

The Pavine and Isopavine Alkaloids

Gözler¹,

Lantz²,

Shamma³

1983

J. Nat. Prod.

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“…(À)-Argemonine has been isolated for the ®rst time from Argemone hispida Gray (Soine & Gisvold, 1944;Schermerhorn & Soine, 1951) and later found in some other Argemone species which occur naturally in the southern regions of North America. The structure of argemonine was determined by Martell et al (1963) and Stermitz et al (1963), and the identity with N-methylpavine, a semisynthetic derivative of papaverine, was proved (Scho È pf, 1949;Battersby & Binks, 1955). The absolute con®guration was established as 6S,12S (C Ï ervinka et al, 1966) and con®rmed by the X-ray study of (À)-argemonine methiodide (Kaneda et al, 1976).…”

Section: Commentmentioning

confidence: 98%