Vallesia dichotoma

Vallesiachotamine (9) (4), isolated first from Vallesia dichotoma Ruiz and Pav., and characterized as a mixture of formyl rotamers (16), proved to be really a mixture of two geometrically isomeric alkaloids vallesiachotamine (9) and isovallesiachotamine (10) (16a). Recently 9 and 10 were isolated from Strychnos... 

The alkaloid dichotamine, C21H24N2O4, occurs in Vallesia dichotoma together with vallesine, aspidospermine, reserpine, and akuammidine. The UV-spectrum was indicative of a 17-methoxy-Aa-formyldihydro-indole structure, and the IR-spectrum showed two carbonyl bands, one... 

Dichotine (68a) and 11-methoxydichotine, bases isolated from Vallesia dichotoma, have structures incorporating several interesting features. The absence of a bond between C(3) and places them in the same relationship to alkaloids of the aspidospermatidine type as iVb-methylpseudostrychnine bears to strychnine the C(12)-Na heterocyclic ring is similar to those in the obscuri-nervine types but the ether link between C(16) and C(19) is novel. The X-ray analysis of the hydrobromide of dichotine, by which the overall structure was established, showed that the transannular Nb-C(3)-carbonyl interaction, evidenced by the spectra of the free base, results in carbonyl oxygen protonation, the salt having a full bond between Nb and C(3). 

Vallesamidine (93) from Vallesia dichotoma is another hovel variant on the aspidosperma theme its structure was derived by X-ray analysis of its methiodide. 

Vallesiachotamine, C2iH22N203 253 decomp. +160° (CHCI3) Vallesia dichotoma Ruiz et Pav. 20... 

The reisolation of a number of simple aspidospermidine derivatives, previously found in A. qtiebracho-bianco Schlecht (Volume VIII), has been reported from Vallesia dichotoma Ruiz et Pav. 12 Table I). Alkaloid 5 from this plant has a mass spectrum similar to that of N -methylaspidospermidine (LXXXc) but differs from this alkaloid in having the C-21 terminal methyl triplet at 0.88 instead of 0.6 ppm. The... 

The occurrence of several of the Picralima bases in other genera has also been reported. Akuammine, for example, is present in Vinca rosea L. Cathar ant hits roseus G. Don (4), and it has also been extracted from the aerial parts of F. major L. (5-7). Akuammieine (IV) has been isolated from the roots of V. rosea (4, S) and 19,20-dihydroakuammicine from the leaves of Pleiocarpapycnantha (K. Schum.) Stapf., var. tubicina (Stapf.) Pichon (9). Akuammidine (V) occurs in the trunk bark of Melodinus australis (F. Mueller) Pierre (Apocyanaceac) (10), in Melodinus scandens Forst. (11), in the leaves of Vallesia dichotoma Ruiz et Pav. (12, 13), and has recently been shown to be one of the major alkaloids of Aspidosperma... 

Floriani has recently examined bark from Aspidosperma quebracho bianco Schlecht f. pendulas Speg, in which he found the known alkaloids, quebrachine (yohimbine) and aspidospermine, as well as Hesse s aspidosamine, C2gH2g02N2, and a new base, aspidospermicine, Ci Hj ON, l-SHjO (1938). Hartmann and Schlittler have shown that the alkaloid vallesine from Vallesia glabra (Apocynaceae) is aspidospermine, and this has been confirmed by Deulofeu et aJ. who have also found it in V. dichotoma. Later Schlittler and Rottenberg by chromatographic analysis of the mother liquors of aspidospermine isolated a second alkaloid for which they used the old name Vallesine (1948). ... 

The related alkaloids ervaticine (15) and apparicine (16a) have been isolated from the leaves of Ervatamia coronaria (85H(23)2975) and from the wood of Vallesia antillana (77MI249), respectively. The latter exhibits high antibacterial activity. Subsequently, 16(S)-hydroxy-16,22-dihydroapparicine (16b) was isolated from the leaves of T. dichotoma (84JNP835). 

Vallesine (XXXVIII) and palosine (XXXIX) are respectively the A,-formyl and Aa-propionyl analogs of aspidospermine (II). Vallesine which occurs in Vallesia glabra and V. dichotoma (Volume II and Ref. 41) has been related to aspidospermine (39, 25) and has therefore structure XXXVIII. 

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