RESUMEN
In a suspension culture of Taxus baccata L. cultivated in a liquid medium according to Ericksson in a 6.21 bioreactor paclitaxel and 8 of its analogues were identified.
Asunto(s)
Antineoplásicos Fitogénicos/biosíntesis , Paclitaxel/biosíntesis , Árboles/metabolismo , Reactores Biológicos , Células Cultivadas , Paclitaxel/análogos & derivados , Árboles/citologíaRESUMEN
Several analogues of (Z)-8-dodecenyl acetate (1a), the major pheromone component of the Oriental fruit moth, Cydia molesta, with chloroformate and lactone functional groups in place of the acetate moiety, were synthesized and investigated for their biological activity at four evaluation levels, i.e. by electroantennography (EAG), electrosensillography (ESG), short-range sexual stimulation and activation in the flight-tunnel. We found very strict requirements on the shape as well as on the electron distribution of the acetate group for a productive interaction with the receptor. The behavioral results showed that, among the analogues investigated, the chloroformate 1b, alken-4-olide 2a and also dodecyl acetate (1c) possess significant (60-85%) inhibitory activities. Based on electrophysiological evidence demonstrating that (i) only 1b is competing with the major pheromone component 1a for the same receptor sites on the male antennal sensilla, (ii) 1c elicits moderate EAG but no ESG responses and (iii) 2a does not produce any electrophysiological response at all, three possible inhibitory mechanisms by which these analogues are acting could be distinguished.
Asunto(s)
Ácidos Grasos Monoinsaturados/química , Mariposas Nocturnas/fisiología , Atractivos Sexuales/química , Animales , Relación Dosis-Respuesta a Droga , Electrofisiología , Masculino , Imitación Molecular , Conducta Sexual Animal , Relación Estructura-ActividadRESUMEN
The sex attractant ofScrobipalpuloides absoluta females is a 90:10 mixture of (3E,8Z,11Z)-3,8,11-tetradecatrien-1-yl acetate and (3E,8Z)-3,8-tetradecadien-1-yl acetate. Tetradecadienyl acetates bearing 8Z,11Z; 3E,8Z; and 3E,11Z double bonds were synthesized by stereospecific procedures; the mass spectral and gas chromatographic properties of the 3E,8Z isomer were found to be congruent with those of the tetradecadienyl acetate fromS. absoluta. In wind tunnel bioassays, a 10:1 mixture of synthetic (3E,8Z,11Z)-3,8,11-tetradecatrien-1-yl acetate and (3E,8Z)-3,8-tetradecadien-1-yl acetate was highly attractive toS. absoluta males. Interestingly, the presence of (8Z,11Z)-8,11-tetradecadien-1-yl acetate (10%) inhibited the response to (3E,8Z,11Z)-3,8,11-tetradecatrien-1-yl acetate completely.
RESUMEN
Silver triflate-promoted condensation of 3,4,6-tri-O-acetyl-2-deoxy-2- phthalimido-beta-D-glucopyranosyl bromide (1) with benzyl 2-acetamido-6-O-benzyl-2-deoxy-3-O- (methoxycarbonyl)methyl-alpha-D-glucopyranoside (4) afforded the key compound, benzyl 2-acetamido-6-O-benzyl-2-deoxy-3-O- (methoxy-carbonyl)methyl-4-O-(3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-b eta-D- glucopyranosyl)-alpha-D-glucopyranoside (5), which after deprotection was transformed into acid 10. Condensation of 10 with the benzyl ester of L-alpha-aminobutanoyl-D-isoglutamine and deisopropylidenation of the product 11 afforded the benzyl ester of N-(2-O-[benzyl 2-acetamido-4-O-(2-acetamido-3-O-benzyloxymethyl-2- deoxy-beta-D-glucopyranosyl)-6-O-benzyl-2,3-dideoxy-alpha-D-glucopyra nosid-3- yl]glycoloyl)-L-alpha-aminobutanoyl-D-isoglutamine (12). Partial O-acylation of 12 and hydrogenolysis of protecting groups gave the 6-O-stearoyl- and 6-O-(2-tetradecylhexadecanoyl)-disaccharide-dipeptides 17 and 18, respectively. Pyrogenicity and adjuvant activity in cell-mediated immunity are reported.