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MS and 1H-NMR Structural Data of Chamazulenecarboxylic Acid.

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626
Cuong, Verm'r-Petri and Tamas
Arch. Pharm.
MS and 'H-NMR Structural Data of Chamazulenecarboxylic Acid
Banh N. Cuong', Gizella Verzar-Petri*' and Joseph T a m a d
I . Institute of Pharmacognosy,Semmelweis Medical University, Budapest (Hung.) H-1085. olliii u.
26
2. Central Chemical Institute of Hungarian Acad. of Sci. Budapest (Hung.) H-1088. Puskin u 7.
Eingegangen am 22. Februar 1979
Chamazulenecarboxylic acid was obtained as an artefact substance from Millefoil (A.
millefolium L.) and other azuleneproducing plant^^.^.^^'). Sfahl has proposed a structure. for
it by chemical evidence and IRspectral data. In this paper MS and 'H-NMRstructural data
not available in the literature are presented.
To obtain chamazulenecarboxylic acid for this purpose the method of Stahl was used
with a substantial improvement which is based on our observation that potassium and
sodium chamazulenecarboxylates can be extracted with ethyl acetate from aqueous
solutions if adequate amounts of alkaline hydroxide has been added, preferably 25-27 %
KOH or NaOH or, after saturation with Na2S04, 3-5 9% KOH or NaOH.
Results and Discussions
1. Chemical a n d GC evidence: conversion into chamazulene
The obtained sample of chamazulenecarboxylicacid gave on heating (80-90°C) with water
chamazulene which was identified by GC2), MS and NMR'). On the G C a chamazulene
peak was observed when it was injected at high injector temperature (130°C or higher).
This suggested that at such high temperatures it is converted instantaneously or nearly so
into chamazulenc. This is in good accordance with Stahl's observations.
2. MS
Under the experimental conditions of MS (high vacuum and high temperature) the amount
of decarboxylation which is observed for similar compounds') was very remarkable. The
relative intensity of the chamazulene peak (m/e = 184) in relation to the molecular ion
peak (m/e = 228). accurate mass measurement gave 228,117 suggesting C15Hl702,
required: (228,115) was strongly dependent on these parameters.The best characteristic
spectrum was achieved at low injector temperature.
MS (70 eV, direct injection, Inj. temp. 60°C.)
MSI70eVI : m/2 = 229 (13 %, i) 228 (65 % M) 213 (4 % M-15),184(56 %, M-44,charnazulene,
decarboxylation), 183 (100 %, M-45)(m' = 145,l) 169 (34 %, chamazulene-15), 168 ( I 1 %,
M-45-15) (m' = 154,2) 167 (11 %), 165 (12%), 155 (14% M-45-28) (m' = 131,2) 153 (18%.
M-45-15-15), 152 (13 %), 141 (7 %), 128 (9 %), 115 (6 %) (Fig.1.).
0 3 ~ 5 ~ ? 3 3 / 7 Y / f l 7 0 7 i ) h ? 6$02,5fl/fl
8 Verlag Chemie. GmbH. Weinheim
1979
312179
Chamazulenecarboxylic Acid
627
chamazulenecorboxylic ocid
Fig. 1: MS-spectrum of chamazulenecarboxylic acid.
'
3. H NMR spectrum
~ 12-Me), 2,64 (s, 14-Me) 2 3 2 (s, 15-Me) 3.90
'H NMR (CDCl3): 6 (ppm) = 1,63 (d, 5 , =~7Hz,
(4.J11.12 = 7&, 11 H), 6,99 (d, J9.8 = 10,5 Hz, 8H), 7,61 (d, J2.3 = 3,5 Hz, 3H) 8,2 ( s , COOH), 8.24
(s, 6H). (Fig. 2.).
Fig. 2: 'H-NMR spectrum of chamazulenecarboxylic acid.
By comparison with the data for chamazulene and guajazulene') the structure deduced by Siahf on
the basis of chemical and IR spectral evidence is confirmed.
We wish to thank Dr. L. Radics and Dr. K. Ujszaszi,Central Research Institute for Chemistry, the
Hungarian Academy of Sciences, for their help in recording and discussing the spectra.
628
Satfler und Schunack
Arch. Pharm.
Experimental
GC:JEOL GC 1100; MS: AEI - MS 902; NMR: VARIAN XL- 100, high resolution, operating in
Fourier transform mode, 100 MHz, int. stand. TMS, CDCI,. Milkfoilflowerheads (A. millefolium ssp.
collina Becker)") with chromosome number 2n = 36 were gathered in the surroundingsof Budapest in
late August of 1975-1976.
50 g of crude drug were treated with about 5 ml of water, kept on waterbath 5-10 min at 8O-YO0C, and
after addition of KOH extracted with ethyl acetate. The solution was subjected to GC, MS and NMR.
References
R. G . Cooks, N. L. Wolfe, J. R. Curtis, E. Petty and R. N. McDonald; J. Org. Chem. 35,4048
(1970).
M. Y. Haggag, A. S. Shalaby and G. Verzhr-Petri; Planta Med. 27,361 (1975).
E.Stahl,Ger.936,206,Dec.7., 1955(CI. 120,25);CA53,712Rg(1959);Ger.937,894,Jan.19,
1956 (CI. 120,25) CA 53,7128 i (1959).
E. Stahl, Chem. Ber. 87,505 (1954).
E. Stahl, Chem. Ber. 87, 1626 (1954).
E. Stahl, Chem. Ber. 87,202 (1954).
G . Verzhr-Petri and N. Cuong: Herba Hung. in press.
G. Vedr-Petri and A. S. Shalaby, Acta Agron. Acad. Sci. Hung. 26, 337 (1977).
[KPh 1511
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