Eight phenolic glycosides have been isolated from the leaves of S. glaucophyllum, one of them being quercetin-3-O-(2G-β-D-apiosylrutinoside).

NewN-acyl-D-glucosylamines (2,3) and 1,1-bis(acylamido)-1-deoxy-D-glucitols (1) have been isolated by applying chromatographic and ionophoretic techniques to the separation of the products from the ammonolysis of penta-O-acetyl-, penta-O-propionyl-, and penta-O-benzoyl-D-glucopyranose. It has been found that, in all cases, acyclic (1) and cyclic (2, 3) products are formed simultaneously. The molar ratio of the cyclic products formed (2+3) to the acyclic ones (1) is higher if the acyl group is aliphatic. The yield ofN-benzoyl-β-D-mannopyranosylamine obtained in the ammonolysis of penta-O-benzoyl-D-mannopyranose is higher than that ofN-benzoyl-β-D-glucopyranosylamine from penta-O-benzoyl-D-glucopyranose, showing the influence of inversion of configuration at C-2. This influence is less pronounced for other acylated monosaccharides that belong to themanno series.

This chapter discusses alkaloids with the typical 1-benzylisoquinoline structure. The study of this class of alkaloids has acquired renewed interest because of the finding of new members of the group, several of which are quaternary bases. The recent discovery of one of the components of the original corpaverine sample (1) has an N-benzyltetrahydroisoquinoline structure, (2) has introduced a new aspect into their research. Biogenetic investigations have also attracted the attention to these alkaloids. Not only the early assumption that the simple benzylisoquinolines originate from aromatic amino acids has been given experimental proof but evidence has been accumulating that some of them are biogenetic precursors of more elaborated natural bases of the morphine, berberine, protopine, and benzophenanthridine groups. One of the chemical reactions given by several phenolic benzyltetrahydroisoquinoline bases that have received more attention currently is their controlled oxidation to produce other bases with more complicated structures like those of the proaporphine, aporpliine, and bisbenzylisoquinoline types. They will be commented on for the natural bases as well as for some non-natural bases that have proved, in some cases, to be susceptible to the conditions of the reaction.

H. A. Priestap, E. A. Ruveda, S. M. Albónico and V. Deulofeu, Chem. Commun. (London), 1967, 754 DOI: 10.1039/C19670000754

By the use of three differently labeled penta-O-benzoyl-D-glucopyranoses, it was possible to detect a partial, benzoyl migration from O-4 to O-6 during the ammonolysis of penta-benzoyl-D-O-glucopyranose in isopropyl alcohol. When the same reaction was applied to a penta-O-benzoyl-aldehydo-D-glucose derivative, a partial migration of a benzoyl group from O-2 to O-6 was also encountered.

The infrared absorption spectra of two glycofuranosylacetamides and their perbenzoates, and of eleven glycopyranosylacylamides and eight esters thereof, are presented and discussed. For comparison, the spectra of thirteen 1,1-bis(acylamido)-1-deoxyalditols and eight esters thereof are also given and discussed. The useful correlations between structure and infrared absorption made by Barker and co-workers for certain carbohydrates, and by Nanasi and co-workers for some N-arylglycosylamines, cannot be extended to the 1-acylamido compounds we have studied. Certain of Verstraeten's correlations may have some diagnostic value.

By the use of three differently labeled penta-O-benzoyl-D-glucopyranoses, it was possible to detect a partial, benzoyl migration from O-4 to O-6 during the ammonolysis of penta-benzoyl-D-O-glucopyranose in isopropyl alcohol. When the same reaction was applied to a penta-O-benzoyl-aldehydo-D-glucose derivative, a partial migration of a benzoyl group from O-2 to O-6 was also encountered.

The N-acetyl-d-glycofuranosylamines produced in the ammonolysis of acetylated d-xylopyranose and acetylated d-glucopyranose have been found to be the α-d anomers. These assignments were obtained by destroying the asymmetry of all of the carbon atoms but the anomeric one (by periodate oxidation) followed by reduction of the resulting aldehydes with sodium borohydride, and comparing the optical rotations of the resulting products with those of known configuration. Application of Hudson's isorotation rules led to the same result. In the ammonolysis of tetra-O-acetyl-β-d-xylopyranose, the known N-acetyl-β-d-xylopyranosylamine is also produced.

AbstractAus der Rinde von Fagara naranjillo (Griseb.) Engler wird eine neue quartäre Benzylisochinolin‐Base, (+)‐Tembetarin (I), isoliert. Sie leitet sich durch N‐Methylierung von der entsprechenden tertiären Base, dem (+)‐Reticulin, ab. I wird durch Oxydation in eine Aporphin‐Base, das (+)‐Laurifolin (IX), übergeführt.

Abstract Fagarine II has been synthesized starting from tetrahydropseudoberberine and its proposed structure (V) confirmed.