๐”– Bobbio Scriptorium
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Further studies of daphniphylline

โœ Scribed by Shosuke Yamamura; Hajime Irikawa; Yoshimasa Hirata


Book ID
104241109
Publisher
Elsevier Science
Year
1967
Tongue
French
Weight
180 KB
Volume
8
Category
Article
ISSN
0040-4039

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โœฆ Synopsis


In the previous paper (1. 2). we rtiported the structure of daphnlphylllne (la). During our studies of the transformation of daphnlphylllne into the other minor alkaloids, which were isolated from tihe same plant, we found some interesting reactions. :.qhen treated with 6N-hydrochloric acid at 8O'C for l&5 min (3), daphnlphylllne as well as desacetyl-daphnlphylllne (lb) was converted into white solid, clesacetyl-isodaphniphylllne (m/e 485 (K+). 455 (K+-301, 2% and 272 (a pair of characteristic peaks, as shown In I); pKzi 3400 (OH), 1753 (flve-membered ring ketone) and 1714 cm-l; no acetoxyl yield. In the M:% spectrum of desacetyl-lsodaphnlphglline, c* r-*%x! group) In quantitative in addition to four (Ia, R' OAc); (Ib, H' OH); (Ic, R' H) methyl signals In the 0.90 -1.15 ppm region, a sharp singJet (acetyl group) at 2.14 ppm was observed instead of a methyl singlet (a) at 1.41 ppm of Ia. Furthermore. there are an AB qua&et (2H, J = 11 cps) centered at 3.49 ppm and multiplets (2H) at the 4.00 -4.30 ppm region. On the basis of the above spectral data (IF., m3? and mass spectra), desacetyl-isodaphnlphylllne should have the structure II or III, which was formed thro.ugh an intermediate IV. Desacetyl-lso-daphr_iphylllne hydrochloride was acetylated with acetic anhydride and pyridlne to xive an isodaphnlphylline hydrochloride. m.p. 197 -19R.5gC (C32H4905N=HC1


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